Dual selective deposition

ABSTRACT

Methods are provided for dual selective deposition of a first material on a first surface of a substrate and a second material on a second, different surface of the same substrate. The selectively deposited materials may be, for example, metal, metal oxide, or dielectric materials.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional PatentApplication No. 61/980,373, filed Apr. 16, 2014, entitled “DUALSELECTIVE DEPOSITION” The disclosure of which is incorporated herein byreference in its entirety.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present application relates to selective deposition of two materialson two different surfaces of a substrate. In particular, a firstmaterial is selectively deposited on a first surface of a substraterelative to a second surface and a second material is selectivelydeposited on the second surface of the substrate relative to the firstsurface.

2. Description of the Related Art

Integrated circuits are currently manufactured by an elaborate processin which various layers of materials are sequentially constructed in apredetermined arrangement on a semiconductor substrate.

The predetermined arrangement of materials on a semiconductor substrateis often accomplished by deposition of a material over the entiresubstrate surface, followed by removal of the material frompredetermined areas of the substrate, such as by deposition of a masklayer and subsequent selective etching process.

In certain cases, the number of steps involved in manufacturing anintegrated surface on a substrate may be reduced by utilizing a dualselective deposition process, wherein a first material is selectivelydeposited on a first surface of a substrate relative to a second surfaceand a second material is selectively deposited on the second surface ofthe substrate relative to the first, without the need, or with reducedneed for subsequent processing. Methods are disclosed herein for dualselective deposition of a first material on a first surface of asubstrate relative to a second surface and a second material on thesecond surface relative to the first surface.

SUMMARY OF THE INVENTION

According to some aspects of the present disclosure, selectivedeposition can be used to deposit a first material on a first surface ofa substrate and a second material on a second surface of the samesubstrate. In some embodiments atomic layer deposition (ALD) typeprocesses are used for selective deposition. In some embodimentschemical vapor deposition (CVD) type processes may be used for selectivedeposition. In some embodiments a metallic material is selectivelydeposited on a first surface of a substrate and a dielectric material isdeposited on a second surface of the same substrate. In some embodimentsa first metallic material is selectively deposited on a first surface ofa substrate and a second metallic material is deposited on a secondsurface of the same substrate.

In some embodiments a first material is selectively deposited on a firstsurface of a substrate and a second material is selectively deposited ona second surface of the same substrate without an airbreak in betweenselective deposition of a first material and selective deposition of asecond material. In some embodiments a first material is selectivelydeposited on a first surface of a substrate and a second material isselectively deposited on a second surface of the same substrate in thesame reactor. In some embodiments a first material is selectivelydeposited on a first surface of a substrate and a second material isselectively deposited on a second surface of the same substrate withoutfurther processing in between selective deposition of a first materialand selective deposition of a second material.

In some embodiments a first material is selectively deposited on a firstsurface of a substrate and a second material is selectively deposited ona second surface of the same substrate, with the selectivity of at least80% for the selective deposition of the first material. In someembodiments a first material is selectively deposited on a first surfaceof a substrate and a second material is selectively deposited on asecond surface of the same substrate, with a selectivity of at least 80%for the selective deposition of the second material.

In some embodiments selective deposition of a first material comprisesat least one deposition cycle comprising alternately and sequentiallycontacting the substrate with a first metal precursor and a secondreactant. In some embodiments selective deposition of a second materialcomprises at least one deposition cycle comprising alternately andsequentially contacting the substrate with a second precursor and asecond reactant. In some embodiments a first material is selectivelydeposited on a first surface of a substrate and a second material isselectively deposited on a second surface of the same substrate, whereinup to 1-50 deposition cycles are carried out for selectively depositingthe first material. In some embodiments a first material is selectivelydeposited on a first surface of a substrate and a second material isselectively deposited on a second surface of the same substrate, whereinup to 1-50 deposition cycles are carried out for selectively depositingthe second material.

In some embodiments the first surface comprises Cu, Si—H, W, Ni, Co, Ruor another noble metal. In some embodiments the first surface is treatedto inhibit deposition of a dielectric material thereon prior toselectively depositing a second dielectric material. In some embodimentsthe first surface is oxidized. In some embodiments the first surface ispassivated. In some embodiments the first surface comprises a metal orsemiconductor material.

In some embodiments the second surface comprises OH, NH_(x) orSH_(x)-terminations. In some embodiments the second surface is thesurface of a dielectric material. In some embodiments the second surfaceis treated to inhibit deposition of the first material thereon prior toselectively depositing the first material on the first surface of thesame substrate. In some embodiments the second surface is treated toprovide OH, NH_(x) or SH_(x)-terminations thereon.

In some embodiments the first material is selected from Sb, Ge, Ru,noble metal, W, Cu, Al, Ni, and Co; and the second material is selectedfrom SbO_(x), GeO₂, BiO_(x), MgO, SiO₂, AlO₂, and TiO₂. In someembodiments the first material comprises Ni, Ge, Fe, Co, or TiO₂; andthe second material is Al or Cu.

In some embodiments a first material is selectively deposited on a firstsurface of a substrate and a second material is selectively deposited ona second surface of the same substrate, wherein selectively depositing asecond material comprises using a passivation precursor. In someembodiments a passivation compound is selected from HCOOH, an alkylaminepassivation compound, or both. In some embodiments passivation can occurduring every deposition cycle of the second material.

BRIEF DESCRIPTION OF THE DRAWINGS

The invention will be better understood from the Detailed Descriptionand from the appended drawings, which are meant to illustrate and not tolimit the invention, and wherein:

FIG. 1A illustrates a process flow for dual selective deposition of afirst material on a first surface of a substrate and a second materialon a second surface of the same substrate;

FIG. 1B illustrates dual selective deposition of a metallic material ona first metal surface and a dielectric material on a second differentsurface according to some embodiments;

FIG. 2 illustrates a process flow for selectively depositing a materialon a first surface of a substrate relative to a second, differentsurface of the same substrate;

FIG. 3A illustrates dual selective deposition of Ru on a first surfaceof a substrate and GeO₂ on a second surface of the same substrateaccording to an embodiment;

FIG. 3B illustrates dual selective deposition of Ru on a first surfaceof a substrate and SiO₂ on a second surface of the same substrateaccording to an embodiment;

FIG. 4 illustrates dual selective deposition of Cu or CuO on a firstsurface of a substrate and GeO₂ on a second surface of the samesubstrate according to an embodiment;

FIG. 5 illustrates dual selective deposition of Sb on a first surface ofa substrate and W on a second surface of the same substrate according toan embodiment;

FIG. 6 illustrates dual selective deposition of Ni or NiO on a firstsurface of a substrate and GeO₂ on a second surface of the samesubstrate according to an embodiment;

FIG. 7A illustrates dual selective deposition of Ni on a first surfaceof a substrate and W on a second surface of the same substrate accordingto an embodiment;

FIG. 7B illustrates dual selective deposition of Ni on a first surfaceof a substrate and W on a second surface of the same substrate accordingto another embodiment;

FIG. 8 illustrates dual selective deposition of Al on a first surface ofa substrate and SiO₂ on a second surface of the same substrate accordingto an embodiment;

DETAILED DESCRIPTION OF SOME EMBODIMENTS

In some situations it is desirable to selectively deposit two differentmaterials on two different surfaces of the same substrate. For example,in some situations a metal is to be deposited on a metal surface of asubstrate and a dielectric is to be deposited on a dielectric surface ofthe same substrate. In other situations a material comprising metal isdeposited on a metal surface of a substrate and a dielectric isdeposited on an oxide, or dielectric surface of the same substrate. Inother situations two different materials are to be deposited on either adielectric OH terminated surface or HF etched Si surface (Si-H orhydrogen terminated silicon) surface of the same substrate. The twomaterials to be deposited can be two different metals to be deposited onadjacent surfaces of the same substrate. The ability to selectivelydeposit each material on the appropriate surface can provide advantages,such as faster processing times and reduced costs. One process forselective CVD of two different materials, including iron adjacent tosacrificial tungsten, is disclosed in Bien et al, Multiple Self-AlignedIron Nanowires by a Dual Selective Chemical Vapor Deposition Process,Electrochemical and Solid-State Letters, 10 (9) H251-H253 (2007), whichis hereby incorporated in its entirety.

Dual selective deposition processes as disclosed herein may be used in avariety of contexts, for example to form capping layers, barrier layers,etch stop layers, sacrificial and/or protective layers or for sealingpores, such as in porous low k materials. In some embodiments a metallicmaterial may be deposited selectively on a first surface of a substratepreferentially over a second, different surface, such as a dielectricsurface of the same substrate; and a dielectric material may beselectively deposited on the second surface relative to the firstsurface. In some embodiments deposition of the metallic materialproceeds first, while in other embodiments deposition of the dielectricmaterial is first. In some embodiments the first surface and the secondsurface are adjacent to each other on the substrate.

One or more surfaces may be treated in order to enhance deposition onone surface relative to one or more different surfaces. In someembodiments a first surface is treated, or activated, in order toenhance deposition on the first surface relative to a second, differentsurface on the same substrate. In some embodiments a second surface istreated, or deactivated, in order to decrease deposition on the secondsurface relative to a first, different surface on the same substrate. Insome embodiments a first surface is treated to enhance deposition and asecond surface is treated to decrease deposition, thereby increasingselective deposition on the first surface relative to the secondsurface. In some embodiments the deactivating treatment does not involveformation of a self-assembled monolayer (SAM) or a similar monolayerhaving a long carbon chain. In some embodiments the deactivatingtreatment is not treatment with an organic agent. For example, in someembodiments the deactivating treatment may be oxidation, reduction orhalogenation, such as chlorination, of the surface. Deactivating cancomprise in-situ passivation from gas phase reactants in the reactorusing the organic group which is present in a precursor used to depositone of the materials, such as dielectric. In case of any passivationeither in-situ passivation with the organic groups or with SAMs, thepassivation is preferably subject to removal at the depositiontemperature with chemistry used to deposit the films or with additionalchemistry, enabling passivation without dedicating a separate step forremoving passivation. For instance passivation can be removed with O₃pulse used to grow the second material or with an additional O₃ pulse.

For example, in some embodiments a dielectric material is deposited on afirst dielectric surface of a substrate relative to a second surface,such as a conductive surface, metal surface, or H-terminated surface ofthe same substrate. The second surface may be oxidized prior to or atthe beginning of the dielectric material deposition in order to decreasedeposition of the dielectric material on the second surface relative tothe dielectric surface. That is, selective deposition on the dielectricsurface is increased relative to the treated second surface. In someembodiments the second surface is passivated, such as by treating thesurface such that it comprises alkylsilyl groups. The passivation mayfacilitate selective deposition on the dielectric surface relative tothe treated second surface. For example, deposition of an oxide on thesecond surface may be inhibited by the passivation. In some embodimentspassivation does not include formation of a SAM or a similar monolayerhaving a long carbon chain on the second surface.

In some embodiments a dielectric surface may be treated to facilitateselective deposition of a metal on a second, different surface relativeto the dielectric surface on the same substrate. For example, thedielectric surface may be treated to provide a hydrophilic OH-terminatedsurface. While an OH-terminated surface can be reactive to certainprecursors, other precursors may not react with this termination. Forexample, an OH-terminated surface can be passive against adsorption ofspecific compounds like Cu-amidinate or ruthenium compounds that havetwo cyclopentadienyl (or derivative thereof) ligands. Thus, in someembodiments OH-termination can be used to inhibit deposition of a metalon a dielectric surface relative to a second, different surface, forexample a conductive surface, metal surface, of H-terminated surface.

In some embodiments a dielectric surface can be passivated to inhibitdeposition of a metal thereon. For example, the dielectric surface maybe contacted with a chemical that provides a silylated (—Si—(CH₃)_(x) or—Si(CH₃)₃) surface or a halogenated surface or a SiH₃ surface. In someembodiments the dielectric surface is chlorinated or fluorinated, suchas a Si—Cl surface. A halogenated surface can be achieved by treatingthe surface with a halide chemical, such as CCl₄ or a metal halide,which is capable of forming volatile metal oxyhalides, such as WF₆,NbF₅, or NbCl₅, and leaving the halide, such as the chloride or fluorideon the surface. The passivation can be used to inhibit deposition of ametal on the dielectric surface relative to a metal surface on the samesubstrate. In some embodiments the passivation chemical is one or moreof trimethylchlorosilane (CH₃)₃SiCl (TMCS), trimethyldimethylaminosilane(CH₃)₃SiN(CH₃)₂ or another type of alkyl substituted silane havingformula R_(4-x)SiX_(x), wherein x is from 1 to 3 and each R canindependently selected to be a C1-C5 hydrocarbon, such as methyl, ethyl,propyl or butyl, preferably methyl, and X is halide or X is anothergroup capable of reacting with OH-groups, such as an alkylamino group—NR₁R₂, wherein each R₁ can be independently selected to be hydrogen orC1-C5 hydrocarbon, preferably methyl or ethyl, R₂ can be independentlyselected to be C1-C5 hydrocarbon, preferably methyl or ethyl, preferablyX is chloride or dimethylamino. In some embodiments the passivationchemical can be a silane compound comprising at least one alkylaminogroup, such as bis(diethylamino)silane, or a silane compound comprisinga SiH₃ group, or silazane, such hexamethyldisilazane (HMDS).

In some embodiments a semiconductor substrate is provided that comprisesa first surface comprising a first material and a second surfacecomprising a second material that is different from the first material.In some embodiments the first surface and the second surface areadjacent to each other. In some embodiments the first surface ishydrophilic and may comprise an OH-terminated surface or a surfacehaving some amount of OH-groups. In some embodiments the first surfacemay be, for example and without limitation, a low-k material, SiO₂ orGeO₂. In some embodiments the second surface is a metal surface. In someembodiments the second surface is a conductive surface. In someembodiments the second surface is an H-terminated surface. For example,the second surface may comprise, for example, Cu, Ni, Co, Al, W, Ru oranother noble metal. Or it may comprise Si-H species(hydrogen-terminated silicon). In some embodiments the second surfacecomprises a metal selected individually from Cu, Ni, Co, Al, W, Ru andother noble metals. In some embodiments the second surface is a Cusurface. In some embodiments the second surface is a Ni surface. In someembodiments the second surface is a Co surface. In some embodiments thesecond surface is an Al surface. In some embodiments the second surfaceis a Ru surface. In some embodiments the second surface comprises anoble metal. In some embodiments the conductive surface comprises anoxide such as CuOx, NiOx, CoOx or RuOx or another noble metal oxide. Insome embodiments a conductive surface may no longer be conductive afterit has been treated. For example, a conductive surface may be treatedprior to or at the beginning of the selective deposition process, suchas by oxidation, and the treated surface may no longer be conductive.For the purposes of the present disclosure, Sb and Ge are considered tobe metals. In some embodiments the first surface is a metal surface,conductive surface, or Si—H surface and the second surface is a surfacecomprising OH-groups, such as a dielectric surface.

In some embodiments a first material is selectively deposited on a firstsurface relative to a second surface, and a second material isselectively deposited on the second surface relative to the firstsurface.

FIG. 1A illustrates an exemplary process flow for selectively depositinga first material on a first surface relative to a second surface and asecond material on a second surface relative to the first surface of thesame substrate. In some embodiments the first surface is a metal surfaceor semiconductor surface, the first material is a metallic material, thesecond surface is a hydrophilic surface, and the second material is adielectric material. In some embodiments the first surface is ahydrophilic surface, the first material is a dielectric material, thesecond surface is a metal layer, and the second material is a metallicmaterial. In other words, the two depositions (metallic and dielectric)can be conducted in either sequence. In some embodiments, the firstmaterial and/or the second material can be deposited by CVD, andselectivity can be achieved through selective decomposition of theprecursor on the surface. In some embodiments at least one of thedepositions is a cyclical vapor phase deposition, particularly atomiclayer deposition (ALD), and selectivity can be achieved throughselective adsorption of one of the reactants. In some embodiments theALD process is not pure ALD process, but some CVD reactions can happen,if the selectivity is retained. For example, complete purging of thereactants from reaction space might not be necessarily needed, but someamount of gas phase reaction might occur and the selectivity can stillbe retained.

In some embodiments a first material is selectively deposited on a firstsurface relative to a second surface and a second material isselectively deposited on a second surface relative to the first surfaceof the same substrate without an airbreak or exposure to air. In someembodiments a first material is selectively deposited on a first surfacerelative to a second surface of the same substrate and a second materialis selectively deposited on a second surface relative to the firstsurface of the same substrate within the same reactor. In someembodiments a dual selective deposition process may comprise selectivedeposition of a first material and selective deposition of a secondmaterial without an airbreak or exposure to air in between selectivedeposition processes. In some embodiments a dual selective depositionprocess is performed wherein a first material is deposited on a firstsurface and a second material is deposited on a second surface of thesame substrate without further processing in between deposition of thefirst material and deposition of the second material. In someembodiments a dual selective deposition process may comprise selectivedeposition of a first material and selective deposition of a secondmaterial without further processing in between.

In some embodiments the process may start when the first material isselectively deposited on the first surface relative to the secondsurface. Prior to deposition, the second surface can be passivated ordeactivated 100, for example as described herein, in order to inhibitdeposition of the first material on the second surface, but in someembodiments such deactivation is not employed. The first surface can beactivated 110, for example as described herein, in order to facilitatedeposition of the first material on the first surface, but in someembodiments such activation is not employed. The first material is thenselectively deposited 120 on the first surface relative to the secondsurface according to the methods disclosed herein.

In some embodiments, selective deposition of the first material on thefirst surface relative to the second surface comprises a vapordeposition process comprising at least one deposition cycle in which thesubstrate is alternately and sequentially contacted with a firstreactant and a second reactant.

In some embodiments, the selective deposition of the first materialcontinues until a desired thickness of first material is obtained on thefirst surface. In some embodiments selective deposition of the firstmaterial continues until a desired number of deposition cycles iscompleted. For example, in some embodiments up to about 1-50 depositioncycles for selectively depositing the first material are carried out.

In some embodiments after a desired thickness of the first material isdeposited (or a desired number of cycles completed), any passivation canbe removed from the second surface (if desired) and the second surfacecan be activated 130, but in some embodiments such activation is notemployed. The first surface can be passivated or deactivated 140, forexample as described herein, in order to inhibit deposition of thesecond material on the first surface, but in some embodiments suchdeactivation is not employed. The second material is then selectivelydeposited on the second surface relative to the first surface 150according to methods disclosed herein. In some embodiments anpassivation can optionally be removed 160 from the first surface (ifdesired).

In some embodiments, selective deposition of the second material on thesecond surface relative to the first surface comprises a vapordeposition process comprising at least one deposition cycle in which thesubstrate is alternately and sequentially contacted with a firstreactant and a second reactant.

In some embodiments, the selective deposition of the second materialcontinues until a desired thickness of second material is obtained onthe second surface. In some embodiments selective deposition of thesecond material continues until a desired number of deposition cycles iscompleted. For example, in some embodiments up to about 1-50 depositioncycles for selectively depositing the second material are carried out.

In some embodiments deposition on the first surface of the substraterelative to the second surface of the substrate, and/or on the secondsurface of the substrate relative to the first surface of the substrateis at least about 90% selective, at least about 95% selective, at leastabout 96%, 97%, 98% or 99% or greater selective. In some embodimentsdeposition only occurs on the first surface and does not occur on thesecond surface or only occurs on the second surface and does not occuron the first surface.

In some embodiments deposition on the first surface of the substraterelative to the second surface of the substrate and/or on the secondsurface of the substrate relative to the first surface is at least about80% selective, which may be selective enough for some particularapplications. In some embodiments the deposition on the first surface ofthe substrate relative to the second surface of the substrate is atleast about 50% selective, which may be selective enough for someparticular application.

In some embodiments an etch may be used subsequent to or in the courseof deposition to remove material that is non-selectively deposited.Although addition of an etch step would typically add cost andcomplexity to the process, in some situations it may be commerciallydesirable, for example if it is overall less expensive than otheroptions. In some embodiments the etch process is preferably isotropicbut may be a wet etch process or a dry etch process. In some embodimentsa dry etch is preferable.

In some ALD embodiments deposition on the first surface of the substraterelative to the second surface of the substrate or on the second surfacerelative to the first surface can be performed up to about 500deposition cycles before losing the selectivity, or up to about 50deposition cycles, or up to about 20 deposition cycles, or up to about10 deposition cycles, or up to about 5 deposition cycles before losingselectivity. In some embodiments even deposition of 1 or 2 cycles beforelosing selectivity can be useful.

A loss of selectivity can be understood to have occurred when theselectivities mentioned above are no longer met. Depending on thespecific circumstances, a loss of selectivity may be considered to haveoccurred when deposition on the first surface of the substrate relativeto the second surface of the substrate or on the second surface relativeto the first surface is less than about 90% selective, less than about95% selective, less than about 96%, 97%, 98% or 99% selective.

In some embodiments deposition on the first surface of the substraterelative to the second surface of the substrate or on the second surfacerelative to the first surface can be performed up to a thickness ofabout 50 nm before losing the selectivity, or up to about 10 nm, or upto about 5 nm, or up to about 3 nm, or up to about 2 nm, or up to about1 nm before losing selectivity. In some embodiments even deposition ofup to 3 Å or 5 Å before losing selectivity can be useful. Depending onthe specific circumstances, a loss of selectivity may be considered tohave occurred when deposition on the first surface of the substraterelative to the second surface of the substrate or on the second surfacerelative to the first surface is less than about 90% selective, lessthan about 95% selective, less than about 96%, 97%, 98% or 99% selectiveor greater.

In some embodiments it may be desirable to selectively deposit a metaloxide and subsequently reduce the metal oxide to metal. Methods forreduction of metal oxides to metals that may be used, such as by the useof a strong reducing agent like HCOOH, are described in U.S. Pat. No.8,536,058, issued Sep. 17, 2013 and in U.S. Pat. No. 7,241,677, issuedJul. 10, 2007, the entire disclosure of each of which is incorporatedherein by reference. In some embodiments a metal oxide is selectivelydeposited on a first surface of a substrate and is reduced to a metalprior to selective deposition of a second material on a second surfaceof the same substrate. In some embodiments a first material isselectively deposited on a first surface of a substrate and a metaloxide is selectively deposited on a second, different surface of thesubstrate. The metal oxide may then be reduced to a metal. In someembodiments a metal oxide is selectively deposited on a first surface ofa substrate and a second material is selectively deposited on a second,different surface of the same substrate prior to reducing the metaloxide to a metal. In some embodiments the reducing agent, such as HCOOH,can also be used for passivation of a surface.

FIG. 1B illustrates an example of dual selective deposition of a firstmetallic material 122 on a first metal surface 121 of a substrate 101,for example a Cu surface, and a second dielectric material 152 on asecond different surface 151 of the same substrate 101, for example SiO₂or a low-k surface.

ALD Type Processes

ALD type processes are based on controlled, self-limiting surfacereactions of precursor chemicals. Gas phase reactions are avoided byalternately and sequentially contacting the substrate with theprecursors. Vapor phase reactants are separated from each other on thesubstrate surface, for example, by removing excess reactants and/orreactant byproducts from the reaction chamber between reactant pulses.

Briefly, a substrate comprising a first surface and second, differentsurface is heated to a suitable deposition temperature, generally atlowered pressure. Deposition temperatures are generally maintained belowthe thermal decomposition temperature of the reactants but at a highenough level to avoid condensation of reactants and to provide theactivation energy for the desired surface reactions. Of course, theappropriate temperature window for any given ALD reaction will dependupon the surface termination and reactant species involved. Here, thetemperature varies depending on the type of film being deposited and ispreferably at or below about 400° C., more preferably at or below about200° C. and most preferably from about 20° C. to about 200° C.

The surface of the substrate is contacted with a vapor phase firstreactant. In some embodiments a pulse of vapor phase first reactant isprovided to a reaction space containing the substrate. In someembodiments the substrate is moved to a reaction space containing vaporphase first reactant. Conditions are preferably selected such that nomore than about one monolayer of the first reactant is adsorbed on thesubstrate surface in a self-limiting manner. The appropriate contactingtimes can be readily determined by the skilled artisan based on theparticular circumstances. Excess first reactant and reaction byproducts,if any, are removed from the substrate surface, such as by purging withan inert gas or by removing the substrate from the presence of the firstreactant.

Purging means that vapor phase precursors and/or vapor phase byproductsare removed from the substrate surface such as by evacuating a chamberwith a vacuum pump and/or by replacing the gas inside a reactor with aninert gas such as argon or nitrogen. Typical purging times are fromabout 0.05 to 20 seconds, more preferably between about 1 and 10, andstill more preferably between about 1 and 2 seconds. However, otherpurge times can be utilized if necessary, such as where highly conformalstep coverage over extremely high aspect ratio structures or otherstructures with complex surface morphology is needed.

The surface of the substrate is contacted with a vapor phase secondgaseous reactant. In some embodiments a pulse of a second gaseousreactant is provided to a reaction space containing the substrate. Insome embodiments the substrate is moved to a reaction space containingthe vapor phase second reactant. Excess second reactant and gaseousbyproducts of the surface reaction, if any, are removed from thesubstrate surface. The steps of contacting and removing are repeateduntil a thin film of the desired thickness has been selectively formedon the first surface of substrate, with each cycle leaving no more thana molecular monolayer. Additional phases comprising alternately andsequentially contacting the surface of a substrate with other reactantscan be included to form more complicated materials, such as ternarymaterials.

As mentioned above, each phase of each cycle is preferablyself-limiting. An excess of reactant precursors is supplied in eachphase to saturate the susceptible structure surfaces. Surface saturationensures reactant occupation of all available reactive sites (subject,for example, to physical size or “steric hindrance” restraints) and thusensures excellent step coverage. Typically, less than one molecularlayer of material is deposited with each cycle, however, in someembodiments more than one molecular layer is deposited during the cycle.

Removing excess reactants can include evacuating some of the contents ofa reaction space and/or purging a reaction space with helium, nitrogenor another inert gas. In some embodiments purging can comprise turningoff the flow of the reactive gas while continuing to flow an inertcarrier gas to the reaction space.

The precursors employed in the ALD type processes may be solid, liquidor gaseous materials under standard conditions (room temperature andatmospheric pressure), provided that the precursors are in vapor phasebefore they are contacted with the substrate surface. Contacting asubstrate surface with a vaporized precursor means that the precursorvapor is in contact with the substrate surface for a limited period oftime. Typically, the contacting time is from about 0.05 to 10 seconds.However, depending on the substrate type and its surface area, thecontacting time may be even higher than 10 seconds. Contacting times canbe on the order of minutes in some cases. The optimum contacting timecan be determined by the skilled artisan based on the particularcircumstances.

The mass flow rate of the precursors can also be determined by theskilled artisan. In some embodiments the flow rate of metal precursorsis preferably between about 1 and 1000 sccm without limitation, morepreferably between about 100 and 500 sccm.

The pressure in a reaction chamber is typically from about 0.01 to about20 mbar, more preferably from about 1 to about 10 mbar. However, in somecases the pressure will be higher or lower than this range, as can bedetermined by the skilled artisan given the particular circumstances.

Before starting the deposition of the film, the substrate is typicallyheated to a suitable growth temperature. The growth temperature variesdepending on the type of thin film formed, physical properties of theprecursors, etc. The growth temperatures are discussed in greater detailbelow in reference to each type of thin film formed. The growthtemperature can be less than the crystallization temperature for thedeposited materials such that an amorphous thin film is formed or it canbe above the crystallization temperature such that a crystalline thinfilm is formed. The preferred deposition temperature may vary dependingon a number of factors such as, and without limitation, the reactantprecursors, the pressure, flow rate, the arrangement of the reactor,crystallization temperature of the deposited thin film, and thecomposition of the substrate including the nature of the material to bedeposited on. The specific growth temperature may be selected by theskilled artisan.

Examples of suitable reactors that may be used include commerciallyavailable ALD equipment such as the F-120® reactor, Eagle® XP8, Pulsar®reactor and Advance® 400 Series reactor, available from ASM America,Inc. of Phoenix, Ariz., ASM Japan KK, Tokyo, Japan and ASM Europe B.V.,Almere, Netherlands. In addition to these ALD reactors, many other kindsof reactors capable of ALD growth of thin films, including CVD reactorsequipped with appropriate equipment and means for pulsing the precursorscan be employed. In some embodiments a flow type ALD reactor is used.Preferably, reactants are kept separate until reaching the reactionchamber, such that shared lines for the precursors are minimized.However, other arrangements are possible, such as the use of apre-reaction chamber as described in U.S. patent application Ser. No.10/929,348, filed Aug. 30, 2004 and 09/836,674, filed Apr. 16, 2001, thedisclosures of which are incorporated herein by reference.

The growth processes can optionally be carried out in a reactor orreaction space connected to a cluster tool. In a cluster tool, becauseeach reaction space is dedicated to one type of process, the temperatureof the reaction space in each module can be kept constant, whichimproves the throughput compared to a reactor in which is the substrateis heated up to the process temperature before each run.

A stand-alone reactor can be equipped with a load-lock. In that case, itis not necessary to cool down the reaction space between each run.

Referring to FIG. 2 and according to some embodiments a substratecomprising a first surface and a second surface is provided at step 210and a material is selectively deposited on a first surface of thesubstrate relative to a second surface by an ALD type deposition process200 comprising multiple cycles, each cycle comprising:

contacting the surface of a substrate with a vaporized first precursorat step 230;

removing excess first precursor and reaction by products, if any, fromthe surface at step 240;

contacting the surface of the substrate with a second vaporized reactantat step 250;

removing from the surface, at step 260, excess second reactant and anygaseous by-products formed in the reaction between the first precursorlayer on the first surface of the substrate and the second reactant,and;

repeating at step 270 the contacting and removing steps until a thinfilm comprising the selectively deposited material of the desiredthickness has been formed.

As mentioned above, in some embodiments one or more surfaces of thesubstrate may be treated in order to enhance deposition on one surfacerelative to one or more different surfaces prior to beginning thedeposition process 200. In FIG. 2 this is indicated by step 220.

Although the illustrated deposition cycle begins with contacting thesurface of the substrate with the first precursor, in other embodimentsthe deposition cycle begins with contacting the surface of the substratewith the second reactant. It will be understood by the skilled artisanthat contacting the substrate surface with the first precursor andsecond reactant are interchangeable in the ALD cycle.

In some embodiments, the reactants and reaction by-products can beremoved from the substrate surface by stopping the flow of firstprecursor while continuing the flow of an inert carrier gas such asnitrogen or argon.

In some embodiments, the reactants and reaction by-products can beremoved from the substrate surface by stopping the flow of secondreactant while continuing the flow of an inert carrier gas. In someembodiments the substrate is moved such that different reactantsalternately and sequentially contact the surface of the substrate in adesired sequence for a desired time. In some embodiments the removingsteps, 240 and 260 are not performed. In some embodiments no reactantmay be removed from the various parts of a chamber. In some embodimentsthe substrate is moved from a part of the chamber containing a firstprecursor to another part of the chamber containing the second reactant.In some embodiments the substrate is moved from a first reaction chamberto a second, different reaction chamber.

Selective Deposition of Metal

As mentioned above, in some embodiments a metal is selectively depositedon a first surface of a substrate relative to a second, differentsurface, such as a dielectric surface of the same substrate. In someembodiments the first surface is a noble metal surface. In someembodiments the first metal surface is an Al, Cu, Ru, Ni, Co, or othernoble metal surface. In some embodiments the first surface comprises ametal selected individually from Cu, Ni, Co, Al, W, Ru and other noblemetals. In some embodiments the first surface is a Cu surface. In someembodiments the first surface is a Ni surface. In some embodiments thefirst surface is a Co surface. In some embodiments the first surface isan Al surface. In some embodiments the first surface is a Ru surface. Insome embodiments the first surface comprises a noble metal.

In some embodiments the first surface comprises metal. In someembodiments the first surface is a conductive surface. In someembodiments the first surface is an H-terminated surface. For example,the first surface may comprise Si-H species (hydrogen-terminatedsilicon). In some embodiments the first surface is not a dielectricsurface. In some embodiments the metal surface comprises an oxide suchas CuOx, NiOx, CoOx or RuOx or another noble metal oxide. In someembodiments a metal surface may no longer be conductive after it hasbeen treated. For example, a metal surface may be treated prior to or atthe beginning of the selective deposition process, such as by oxidation,and the treated surface may no longer be conductive. In some embodimentsthe second, non-metal surface, is a hydrophilic, OH-terminated surfaceor contains some amount of OH-groups. In some embodiments the second,non-metal, surface is a dielectric surface. In some embodiments thesecond, non-metal surface is SiO₂, GeO₂, or low-k material.

In some embodiments the second, non-metal surface is deactivated, suchas by a treatment to provide a surface on which metal deposition isinhibited. In some embodiments deactivation may comprise treatment witha passivation chemical. In some embodiments the deactivation treatmentcan occur prior to the deposition of a metal on a first metal surface.In some embodiments the deactivation treatment may be an in situdeactivation treatment. In some embodiments deactivation of thehydrophilic surface may comprise replacing at least OH-groups with othergroups. In some embodiments deactivation can include treatment toincrease the amount of OH-groups on the second, non-metal, surface.

In some embodiments the second surface is deactivated, such as bypassivation prior to deposition of a metal. In some embodimentsdeactivation of the second surface may comprise replacing at least someOH-groups with other groups. In some embodiments the second surface istreated with a passivation chemical to form a passivated surface. Forexample, the second surface may be silylated or halogenated, such aschlorinated or fluorinated, prior to deposition of the metal. In someembodiments the second surface may be treated to form a silylatedsurface, such as a silylated —Si—(CH₃)_(x) or —Si(CH₃)₃ surface. In someembodiments the second surface may be treated to form a halogenatedsurface, such as a chlorinated or fluorinated surface. For example, thehalogenated surface may be a Si—Cl surface. In some embodiments thesecond surface may be treated to provide a H-terminated surface, forexample a —SiH₃ surface. For example, in some embodiments the secondsurface may be contacted with a chemical that provides a —SiH₃ surface.

In some embodiments deposition on the first surface of the substraterelative to the second surface of the substrate is at least about 90%selective, at least about 95% selective, at least about 96%, 97%, 98% or99% or greater selective. In some embodiments deposition only occurs onthe first surface and does not occur on the second surface. In someembodiments deposition on the first surface of the substrate relative tothe second surface of the substrate is at least about 80% selective,which may be selective enough for some particular applications. In someembodiments deposition on the first surface of the substrate relative tothe second surface of the substrate is at least about 50% selective,which may be selective enough for some particular applications.

Selective Deposition of Sb by ALD

In some embodiments Sb is selectively deposited on a first surfacecomprising a metal on a substrate comprising a first surface and asecond, different surface. In some embodiments the first surface is ahydrophilic surface. In some embodiments the first surface is adielectric surface. In some embodiments, Sb is selectively deposited ona first surface of a substrate, such as a Cu, Ni, Co, Al, W, Ru, oranother noble metal surface relative to a second, different surface ofthe same substrate. In some embodiments Sb is selectively deposited onCu surface, relative to a second, different surface. In some embodimentsSb is selectively deposited on a Ni surface, relative to a second,different surface. In some embodiments Sb is selectively deposited on aCo surface, relative to a second, different surface. In some embodimentsSb is selectively deposited on a Al surface, relative to a second,different surface. In some embodiments Sb is selectively deposited on aRu surface, relative to a second, different surface. In some embodimentsSb is selectively deposited on a noble metal surface, relative to asecond, different surface.

In some embodiments the first surface comprises metal. In someembodiments the first surface is a conductive surface. In someembodiments the first surface is an H-terminated surface. For example,the first surface may comprise Si-H species (hydrogen-terminatedsilicon).

In some embodiments Sb is selectively deposited on a first hydrophilicsurface of a substrate, relative to a second, different surface of thesame substrate. In some embodiments the first hydrophilic surface maycomprise at least some OH-groups. In some embodiments the first surfaceis a —NH_(x) terminated surface. In some embodiments the first surfaceis a —SH_(x) terminated surface. In some embodiments the hydrophilicsurface is a dielectric surface. In some embodiments the hydrophilicsurface may comprise SiO₂, a low k material, or GeO₂. In someembodiments the second, different surface comprises a metal surface or adielectric surface comprising Si—H surface terminations as describedherein.

In some embodiments the metal surface comprises an oxide such as CuOx,NiOx, CoOx or RuOx or another noble metal oxide. In some embodiments ametal surface may no longer be conductive after it has been treated. Forexample, a metal surface may be treated prior to or at the beginning ofthe selective deposition process, such as by oxidation, and the treatedsurface may no longer be conductive.

In some embodiments the second surface is a hydrophilic surface. In someembodiments the hydrophilic surface may comprise at least someOH-groups. In some embodiments the second surface is a —NH_(x)terminated surface. In some embodiments the second surface is a —SH_(x)terminated surface. In some embodiments the hydrophilic surface is adielectric surface. In some embodiments the hydrophilic surface maycomprise SiO₂, a low k material, or GeO₂.

As previously discussed, in some embodiments a hydrophilic surface istreated to facilitate selective deposition of Sb relative to thehydrophilic surface. For example, a surface may be treated to provide ahydrophilic OH-terminated surface. In some embodiments a hydrophilicOH-terminated surface may be treated to increase the amount of OH-groupson the surface. For example, the dielectric surface may be exposed toH2O vapor in order to increase the number of OH-groups at the surface.Another example includes exposing a dielectric surface to a carrier gasthat has flowed through a bubbler at a temperature of between 25° C. and40° C. In some embodiments the dielectric surface is exposed to air inorder to provide a hydrophilic surface that comprises at least someOH-groups. In some embodiments a hydrophilic surface is not treatedprior to deposition.

In some embodiments the hydrophilic surface is deactivated, such as bypassivation prior to deposition of Sb. In some embodiments deactivationof the hydrophilic surface may comprise replacing at least OH-groupswith other groups. In some embodiments the hydrophilic dielectricsurface is treated with a passivation chemical to form a passivatedsurface. For example, the hydrophilic surface may be silylated orhalogenated, such as chlorinated or fluorinated, prior to deposition ofthe Sb. In some embodiments the hydrophilic surface may be treated toform a silylated surface, such as a silylated —Si—(CH₃)_(x) or —Si(CH₃)₃surface. In some embodiments the hydrophilic surface may be treated toform a halogenated surface, such as a chlorinated or fluorinatedsurface. For example, the halogenated surface may be a Si—Cl surface. Insome embodiments the hydrophilic surface may be treated to provide aH-terminated surface, for example a —SiH₃ surface. For example, in someembodiments the hydrophilic surface may be contacted with a chemicalthat provides a H-terminated surface. In some embodiments thehydrophilic surface may be contacted with HF to provide a H-terminatedsurface.

In some embodiments the passivation chemical is one or more oftrimethylchlorosilane (CH₃)₃SiCl (TMCS), trimethyldimethylaminosilane(CH₃)₃SiN(CH₃)₂ or another type of alkyl substituted silane havingformula R_(4-x)—SiX_(x), wherein x is from 1 to 3 and each R canindependently selected to be a C1-C5 hydrocarbon, such as methyl, ethyl,propyl or butyl, preferably methyl, and X is halide or X is anothergroup capable of reacting with OH-groups, such as an alkylamino group—NR₁R₂, wherein each R₁ can be independently selected to be hydrogen orC1-C5 hydrocarbon, preferably methyl or ethyl, R₂ can be independentlyselected to be C1-C5 hydrocarbon, preferably methyl or ethyl, preferablyX is chloride or dimethylamino. In some embodiments the passivationchemical can be a silane compound comprising at least one alkylaminogroup, such as bis(diethylamino)silane, or a silane compound comprisinga SiH₃ group, or silazane, such hexamethyldisilazane (HMDS).

In some embodiments Sb deposition on the first surface of the substraterelative to the second surface of the substrate is at least about 90%selective, at least about 95% selective, at least about 96%, 97%, 98% or99% or greater selective. In some embodiments Sb deposition only occurson the first surface and does not occur on the second surface. In someembodiments Sb deposition on the first surface of the substrate relativeto the second surface of the substrate is at least about 80% selective,which may be selective enough for some particular applications. In someembodiments deposition on the first surface of the substrate relative tothe second surface of the substrate is at least about 50% selective,which may be selective enough for some particular applications.

In some embodiments Sb is selectively deposited by an ALD type process.In some embodiments Sb is selectively deposited without the use ofplasma. In some embodiments deposition may be carried out, for example,as described in U.S. Publication No. 2012/0329208 (U.S. application Ser.No. 13/504,079), which is hereby incorporated by reference.

In some embodiments a substrate comprising a first surface and a secondsurface is provided and a metal, here Sb, is selectively deposited on afirst surface of a substrate by an ALD type deposition processcomprising multiple cycles, each cycle comprising:

contacting the surface of a substrate with a vaporized first metalprecursor, for example SbCl₃;

removing excess metal precursor and reaction by products, if any, fromthe surface;

contacting the surface of the substrate with a second vaporizedreactant, for example Sb(SiEt₃)₃;

removing from the surface, excess second reactant and any gaseousby-products formed in the reaction between the metal precursor layer onthe first surface of the substrate and the second reactant, and;

repeating at the contacting and removing steps until a metal, here Sb,thin film of the desired thickness has been formed.

As mentioned above, in some embodiments one or more surfaces of thesubstrate may be treated in order to enhance deposition on one surfacerelative to one or more different surfaces prior to beginning thedeposition process. In some embodiments the second, non-metal surfacecan be treated to provide an OH-terminated surface, or can bedeactivated, such as by passivation, prior to deposition of the metal,here Sb.

Although the illustrated Sb deposition cycle begins with contacting thesurface of the substrate with the first Sb precursor, in otherembodiments the deposition cycle begins with contacting the surface ofthe substrate with the second reactant. It will be understood by theskilled artisan that contacting the substrate surface with the first Sbprecursor and second reactant are interchangeable in the ALD cycle.

In some embodiments, the reactants and reaction by-products can beremoved from the substrate surface by stopping the flow of the firstprecursor while continuing the flow of an inert carrier gas such asnitrogen or argon.

In some embodiments, the reactants and reaction by-products can beremoved from the substrate surface by stopping the flow of secondreactant while continuing the flow of an inert carrier gas such asnitrogen or argon.

In some embodiments the substrate is moved such that different reactantsalternately and sequentially contact the surface of the substrate in adesired sequence for a desired time. In some embodiments the removingsteps are not performed. In some embodiments no reactant may be removedfrom the various parts of a chamber. In some embodiments the substrateis moved from a part of the chamber containing a first precursor toanother part of the chamber containing the second reactant. In someembodiments the substrate is moved from a first reaction chamber to asecond, different reaction chamber.

In some embodiments the second reactant can comprise a Sb precursor. Insome embodiments the second reactant is a second Sb precursor. In someembodiments the second reactant is a second Sb precursor that isdifferent from the first Sb precursor.

In some embodiments the first Sb precursor has a formula of SbX₃,wherein X is a halogen element. In some embodiments the first Sbprecursor is SbCl₃, SbBr₃ or SbI₃.

In some embodiments, the second reactant is not an oxygen source. Theterm “oxygen source” refers to reactants that comprise oxygen, such aswater, ozone, alcohol, oxygen atoms, oxygen plasma and oxygen radicals,typically used in ALD for depositing metal oxides. In some embodimentsthe second reactant is not water, ozone or alcohol.

In some embodiments the second reactant to be used in combination withthe Sb precursors disclosed herein is not an alkylaminogermaniumprecursor, such as tetraalkylminogermanium, or organotelluriumprecursor. In some embodiments the second reactant to be used incombination with the Sb precursors disclosed herein is not achalcogenide precursor. In some embodiments the second reactant to beused in combination with the Sb precursors disclosed herein does notcontain plasma or an excited species. In some embodiments the secondreactant to be used in combination with the Sb precursors disclosedherein does not contain nitrogen. In some embodiments the secondreactant to be used in combination with the Sb precursors disclosedherein is not an alkoxide substituted precursor. In some embodiments thesecond reactant to be used in combination with the Sb precursorsdisclosed herein is not an amino substituted precursor. In someembodiments the second reactant to be used in combination with the Sbprecursors disclosed herein is not an alkyl substituted precursor. Insome embodiments the second reactant to be used in combination with theSb precursors disclosed herein does not contain a direct Sb—C bond.

The Sb center atoms of the Sb precursors disclosed herein can be bondedto Si, Ge, or Sn atoms. Sb is more electronegative than Si, Ge or Sn,which will create polarity in bonds and thus a partial negative chargeon the Sb center atoms of the Sb precursors disclosed herein. In someembodiments, the Sb center atoms can have a negative oxidation state. Itis believed, although not being bound to any theory, that the slightpartial negative charge of the center atom in the precursors disclosedherein, for example the slight partial negative charge of Sb inSb(SiEt₃)₃, combined with the partial positive charge of the center atomin the other precursor, for example the partial positive charge of Sb inSbCl₃, makes the precursor combination successful and film depositionpossible.

In some embodiments the second reactant to be used in combination withthe Sb precursors disclosed herein is not a reducing agent, such ashydrogen, H₂/plasma, amine, imine, hydrazine, silane, silylchalcogenide, germane, ammonia, alkane, alkene or alkyne. As used hereina reducing agent refers to a compound capable of reducing an atom of theother reactant, usually the atom which will be deposited in the film inan ALD process and sometimes to elemental form. At the same time thereducing agent can be oxidized. It may be noted that with oxidativechemistry, for example with an oxidation agent, it is also possible toproduce elemental films if the formal oxidation states of the atom,which will be deposited, are negative in the other precursor. In someembodiments the Sb precursors disclosed herein act as a reducing agentin an ALD process.

In some embodiments the second reactant to be used in combination withSb precursors disclosed herein is an oxidizing precursor, such as SbCl₃.Preferably the oxidizing precursor is not water, alcohol or ozone. Asused herein an oxidizing precursor is a precursor, which has a partialpositive charge in the center atom of the molecule, such as Sb in caseof SbCl₃, and thus center atoms can be considered to have positiveoxidation states. The partial positive charge of the oxidizingprecursors will be decreased in the deposited film i.e. the center atomof the molecule can be considered to be somewhat reduced although noreal oxidation state increase has happened. In some embodiments theantimony deposition cycle only uses two reactive compounds.

Preferably, the second reactant is a Sb precursor with a formula ofSb(SiR1R2R3)₃, wherein R1, R2, and R3 are alkyl groups comprising one ormore carbon atoms. The R1, R2, and R3 alkyl groups can be selected basedon the desired physical properties of the precursor such as volatility,vapor pressure, toxicity, etc.

In some embodiments the first Sb precursor is SbCl₃ and the second Sbprecursor is Sb(SiEt₃)₃.

The substrate temperature during selective Sb thin film deposition ispreferably less than 250° C. and more preferably less than 200° C. andeven more preferably below 150° C.

Pressure of the reactor can vary much depending from the reactor usedfor the depositions. Typically reactor pressures are below normalambient pressure.

The skilled artisan can determine the optimal reactant evaporationtemperatures based on the properties of the selected precursors. Theevaporation temperatures for the second Sb precursor, such asSb(SiEt₃)₃, or Sb(SiMe₃)₃ which can be synthesized by the methodsdescribed herein, is typically about 85° C., or about room temperature,respectively. The evaporation temperature for the first Sb precursor,such as SbCl₃, is typically about 30° C. to 50° C.

The skilled artisan can determine the optimal reactant contact timesthrough routine experimentation based on the properties of the selectedprecursors and the desired properties of the deposited Sb thin film.Preferably the first and second Sb reactants are contacted for about0.05 to 10 seconds, more preferably about 0.2 to 4 seconds, and mostpreferably about 1 to 2 seconds. The removal steps in which excessreactant and reaction by-products, if any, are removed are preferablyabout 0.05 to 10 seconds, more preferably about 0.2-4 seconds, and mostpreferably 1 to 2 seconds in length.

The growth rate of the elemental Sb thin films will vary depending onthe reaction conditions. As described below, in initial experiments, thegrowth rate varied between about 0.3 and about 0.5 Å/cycle.

As previously discussed, in some embodiments Sb deposition on the firstsurface of the substrate relative to the second surface of the substrateis at least about 90% selective, at least about 95% selective, at leastabout 96%, 97%, 98% or 99% or greater selective. In some embodiments Sbdeposition only occurs on the first surface and does not occur on thesecond surface. In some embodiments Sb deposition on the first surfaceof the substrate relative to the second surface of the substrate is atleast about 80% selective, which may be selective enough for someparticular applications. In some embodiments deposition on the firstsurface of the substrate relative to the second surface of the substrateis at least about 50% selective, which may be selective enough for someparticular applications.

Sb Precursors

Precursors that may be used as a first or second reactant in ALD typeselective deposition processes for Sb disclosed herein are discussedbelow.

In some embodiments the Sb precursors disclosed herein can be the firstSb precursor. In some embodiments the Sb precursors disclosed herein canbe the second reactant. In some embodiments the Sb precursors disclosedherein can be the first Sb precursor or the second reactant. In someembodiments the Sb precursors disclosed herein can be the first Sbprecursor and the second reactant. In some embodiments the first Sbprecursor is a Sb precursor disclosed herein and the second reactant isa second, different Sb precursor disclosed herein.

[In some embodiments Sb precursors that may be used as the first Sbprecursor, the second reactant, or both include, Sb halides, such asSbCl₃ and SbI₃, Sb alkoxides, such as Sb(OEt)₃ and Sb amides.

In some embodiments a Sb precursor has Sb bound to at least one siliconatom, preferably at least to two silicon atoms and more preferably Sb isbound to three silicon atoms. For example it can have a general formulaof Sb(AR1R2R3)₃, wherein A is Si or Ge, and R1, R2, and R3 are alkylgroups comprising one or more carbon atoms. Each of the R1, R2 and R3ligands can be selected independently of each other. The R1, R2, and R3alkyl groups can be selected independently of each other in each ligandbased on the desired physical properties of the precursor such asvolatility, vapor pressure, toxicity, etc. In some embodiments, R1, R2and/or R3 can be hydrogen, alkenyl, alkynyl or aryl groups. In someembodiments, R1, R2, R3 can be any organic groups containingheteroatoms, such as N, O, F, Si, P, S, Cl, Br or I. In some embodimentsR1, R2, R3 can be halogen atoms. In some embodiments the Sb precursorhave a general formula of Sb(SiR1R2R3)₃, wherein R1, R2, and R3 arealkyl groups comprising one or more carbon atoms. In some embodiments,R1, R2 and/or R3 can be unsubstituted or substituted C1-C2 alkyls, suchas methyl or ethyl groups. The R1, R2, and R3 alkyl groups can beselected independently of each other in each ligand based on the desiredphysical properties of the precursor such as volatility, vapor pressure,toxicity, etc. In some embodiments the Sb precursor is Sb(SiMe₂tBu)₃. Inother embodiments the precursor is Sb(SiEt₃)₃ or Sb(SiMe₃)₃. In morepreferred embodiments the precursor has a Sb—Si bond and most preferablya three Si—Sb bond structure.

In some embodiments a Sb precursor has a general formula ofSb[Al(X1R1R2R3)₃][A2(X2R4R5R6)₃][A3(X3R7R8R9)₃] wherein Al, A2, A3 canbe independently selected to be Si or Ge and wherein R1, R2, R3, R4, R5,R6, R7, R8, and R9, can be independently selected to be alkyl, hydrogen,alkenyl, alkynyl or aryl groups. In some embodiments, R1, R2, R3, R4,R5, R6, R7, R8, and R9 can be any organic groups containing alsoheteroatoms, such as N, O, F, Si, P, S, Cl, Br or I. In some embodimentsone or more R1, R2, R3, R4, R5, R6, R7, R8, and R9 can be halogen atoms.In some embodiments X1, X2, and X3 can be Si, Ge, N, or O. In someembodiments X1, X2, and X3 are different elements. In embodiments when Xis Si then Si will be bound to three R groups, for exampleSb[Si(SiR1R2R3)₃][Si(SiR4R5R6)₃][Si(SiR7R8R9)₃]. In embodiments when Xis N then nitrogen will only be bound to two R groupsSb[Si(NR1R2)3][Si(NR3R4)3][Si(NR5R6)3]. In embodiments when X is O, theoxygen will only be bound to one R group, for exampleSb[Si(OR1)₃][Si(OR2)₃][Si(OR3)₃]. R1, R2, R3, R4, R5, R6, R7, R8, and R9groups can be selected independently of each other in each ligand basedon the desired physical properties of the precursor such as volatility,vapor pressure, toxicity, etc.

Selective Deposition of Ge on Metal

In some embodiments Ge is selectively deposited on a first surfacerelative to a different surface of the same substrate. In someembodiments Ge is selectively deposited on a metal surface, such as aNi, Co, Cu, Al, Ru, or other noble metal surface relative to a differentsurface of the same substrate, such as a passivated surface. In someembodiments the first surface is a hydrophilic surface. In someembodiments the first surface is a dielectric surface. In someembodiments Ge is selectively deposited on a Cu surface, relative to asecond, different surface. In some embodiments Ge is selectivelydeposited on a Ni surface, relative to a second, different surface. Insome embodiments Ge is selectively deposited on a Co surface, relativeto a second, different surface. In some embodiments Ge is selectivelydeposited on a Al surface, relative to a second, different surface. Insome embodiments Ge is selectively deposited on a Ru surface relative toa second, different surface. In some embodiments Ge is selectivelydeposited on a noble metal relative to a second, different surface.

In some embodiments the metal surface comprises an oxide such as CuOx,NiOx, CoOx or RuOx or another noble metal oxide. In some embodiments ametal surface may no longer be conductive after it has been treated. Forexample, a metal surface may be treated prior to or at the beginning ofthe selective deposition process, such as by oxidation, and the treatedsurface may no longer be conductive.

In some embodiments Ge is selectively deposited on a surface comprisingmetal, such as Ni, Co, Cu, Al, Ru, or other noble metal relative to adifferent surface of the same substrate. In preferred embodiments,however, Ge is selectively deposited on a dielectric, OH terminatedsurface through decomposition of for instance Ge alkoxide precursor,relative to Si-H terminated surface of the same substrate. Thehydrophilic surface may comprise at least some OH-groups. In someembodiments the hydrophilic surface is a dielectric surface. In someembodiments the hydrophilic surface may comprise Si-O H or Ge—OH surfacegroups, SiO₂, a low k material, or GeO₂. In some embodiments Ge isselectively deposited by a cyclical deposition process. For example, thesubstrate may be alternately and sequentially contacted with a germaniumreactant, such as a germanium alkoxide or alkylamine and a secondreactant, such as a nitrogen reactant like NH₃. In some embodiments theGe reactant is one of Ge(OEt)₄, Ge(OMe)₄, Ge(O^(i)Pr)₄ or Ge(O^(t)Bu)₄.

In some embodiments the first surface comprises metal. In someembodiments the first surface is a conductive surface. In someembodiments the first surface is an H-terminated surface. For example,the first surface may comprise Si-H species (hydrogen-terminatedsilicon).

In some embodiments Ge is selectively deposited by a process such asthat described in U.S. application Ser. No. 14/135,383, filed Dec. 19,2013, which is hereby incorporated by reference.

In some embodiments Ge deposition on the first surface of the substraterelative to the second surface of the substrate is at least about 90%selective, at least about 95% selective, at least about 96%, 97%, 98% or99% or greater selective. In some embodiments Ge deposition only occurson the first surface and does not occur on the second surface. In someembodiments Ge deposition on the first surface of the substrate relativeto the second surface of the substrate is at least about 80% selective,which may be selective enough for some particular applications. In someembodiments deposition on the first surface of the substrate relative tothe second surface of the substrate is at least about 50% selective,which may be selective enough for some particular applications.

In some embodiments the second surface is a hydrophilic surface. In someembodiments the hydrophilic surface may comprise at least someOH-groups. In some embodiments the second surface is a —NH_(x)terminated surface. In some embodiments the second surface is a —SH_(x)terminated surface. In some embodiments the hydrophilic surface is adielectric surface. In some embodiments the hydrophilic surface maycomprise SiO₂, a low k material, or GeO₂. In some embodiments Ge isselectively deposited by an ALD type deposition process. For example,the substrate may be alternately and sequentially contacted with agermanium reactant, such as a germanium alkoxide or alkylamine and asecond reactant, such as a nitrogen reactant like NH₃.

As previously discussed, in some embodiments the second surface istreated to facilitate selective deposition of Ge on a metal surfacerelative to the second surface. For example, the second surface may betreated to provide a hydrophilic OH-terminated surface. In someembodiments a hydrophilic OH-terminated surface may be treated toincrease the amount of OH-groups on the surface. For example, thedielectric surface may be exposed to H2O vapor in order to increase thenumber of OH-groups at the surface. Another example includes exposing adielectric surface to a carrier gas that has flowed through a bubbler ata temperature of between 25° C. and 40° C. In some embodiments thedielectric surface is exposed to air in order to provide a hydrophilicsurface that comprises at least some OH-groups. In some embodiments ahydrophilic surface is not treated prior to deposition.

In some embodiments the hydrophilic surface is deactivated, such as bypassivation prior to deposition of Ge. In some embodiments deactivationof the hydrophilic surface may comprise replacing at least OH-groupswith other groups. In some embodiments the hydrophilic dielectricsurface is treated with a passivation chemical to form a passivatedsurface. For example, the hydrophilic surface may be silylated orhalogenated, such as chlorinated or fluorinated, prior to deposition ofthe Ge. In some embodiments the hydrophilic surface may be treated toform a silylated surface, such as a silylated —Si—(CH₃)— or —Si(CH₃)₃surface. In some embodiments the hydrophilic surface may be treated toform a halogenated surface, such as a chlorinated or fluorinatedsurface. For example, the halogenated surface may be a Si—Cl surface. Insome embodiments the hydrophilic surface may be treated to provide aH-terminated surface, for example a —SiH₃ surface. For example, in someembodiments the hydrophilic surface may be contacted with a chemicalthat provides a H-terminated surface.

As noted above, processes described herein enable use of ALD typedeposition techniques to selectively deposit germanium. The ALD typedeposition process is mostly surface-controlled (based on controlledreactions at the first substrate surface) and thus has the advantage ofproviding high conformality at relatively low temperatures. However, insome embodiments, the germanium precursor may at least partiallydecompose. Accordingly, in some embodiments the ALD type processdescribed herein is a pure ALD process in which no decomposition ofprecursors is observed. In other embodiments reaction conditions, suchas reaction temperature, are selected such that a pure ALD process isachieved and no precursor decomposition takes place.

Because of the variability in decomposition temperatures of differentcompounds, the actual reaction temperature in any given embodiment maybe selected based on the specifically chosen precursors. In someembodiments the deposition temperature is below about 600° C. In someembodiments the deposition temperature is below about 500° C. In someembodiments the deposition temperature is below about 450° C. In someembodiments the deposition temperature is preferably below about 400° C.and even, in some cases, below about 375° C.

In some embodiments Ge is selectively deposited on a first surface of asubstrate relative to a second, different surface of the substrate by anALD type process comprising alternately and sequentially contacting thesubstrate with a first Ge precursor and a second reactant.

In some embodiments a substrate comprising a first surface and a secondsurface is provided and a metal, here Ge, is selectively deposited on afirst surface of a substrate by an ALD type deposition processcomprising multiple cycles, each cycle comprising:

contacting the surface of a substrate with a vaporized first metalprecursor, for example TDMAGe;

removing excess metal precursor and reaction by products, if any, fromthe surface;

contacting the surface of the substrate with a second vaporizedreactant, for example NH₃;

removing from the surface excess second reactant and any gaseousby-products formed in the reaction between the metal precursor layer onthe first surface of the substrate and the second reactant, and;

repeating the contacting and removing steps until a metal, here Ge, thinfilm of the desired thickness has been formed.

As mentioned above, in some embodiments one or more surfaces of thesubstrate may be treated in order to enhance deposition on one surfacerelative to one or more different surfaces prior to beginning thedeposition process. In some embodiments the second, non-metal surfacecan be treated to provide an OH-terminated surface, or can bedeactivated, such as by passivation, prior to deposition of the metal,here Ge.

Although the illustrated Ge deposition cycle begins with contacting thesubstrate with the first Ge precursor, in other embodiments thedeposition cycle begins with contacting the substrate with the secondreactant. It will be understood by the skilled artisan that contactingthe substrate surface with the first Ge precursor and second reactantare interchangeable in the ALD cycle.

When the Ge precursor contacts the substrate, the Ge precursor may format least a monolayer, less than a monolayer, or more than a monolayer.

In some embodiments, a carrier gas is flowed continuously to a reactionspace throughout the deposition process. In some embodiments in eachdeposition cycle the first germanium precursor is pulsed into a reactionchamber. In some embodiments excess germanium precursor is then removedfrom the reaction chamber. In some embodiments, the carrier gascomprises nitrogen. In some embodiments a separate purge gas isutilized.

In some embodiments, the reactants and reaction by-products can beremoved from the substrate surface by stopping the flow of secondreactant while continuing the flow of an inert carrier gas. In someembodiments the substrate is moved such that different reactantsalternately and sequentially contact the surface of the substrate in adesired sequence for a desired time. In some embodiments the removingsteps are not performed. In some embodiments no reactant may be removedfrom the various parts of a chamber. In some embodiments the substrateis moved from a part of the chamber containing a first precursor toanother part of the chamber containing the second reactant. In someembodiments the substrate is moved from a first reaction chamber to asecond, different reaction chamber.

The Ge precursor employed in the ALD type processes may be solid,liquid, or gaseous material under standard conditions (room temperatureand atmospheric pressure), provided that the Ge precursor is in vaporphase before it is contacted with the substrate surface.

Contacting a substrate surface with a vaporized precursor means that theprecursor vapor is in contact with the substrate surface for a limitedperiod of time. Typically, the contacting time is from about 0.05 to 10seconds. However, depending on the substrate type and its surface area,the contacting time may be even higher than 10 seconds. contacting timescan be on the order of minutes in some cases. The optimum contactingtime can be determined by the skilled artisan based on the particularcircumstances. In some embodiments the substrate is moved such thatdifferent reactants alternately and sequentially contact the surface ofthe substrate in a desired sequence for a desired time. In someembodiments the substrate is moved from a first reaction chamber to asecond, different reaction chamber. In some embodiments the substrate ismoved within a first reaction chamber.

In some embodiments, for example for a 300 mm wafer in a single waferreactor, the surface of a substrate is contacted with Ge precursor forfrom about 0.05 seconds to about 10 seconds, for from about 0.1 secondsto about 5 seconds or from about 0.3 seconds to about 3.0 seconds.

The surface of the substrate may be contacted with a second reactant forfrom about 0.05 seconds to about 10 seconds, from about 0.1 seconds toabout 5 seconds, or for from about 0.2 seconds to about 3.0 seconds.However, contacting times for one or both reactants can be on the orderof minutes in some cases. The optimum contacting time for each reactantcan be determined by the skilled artisan based on the particularcircumstances.

As mentioned above, in some embodiments the Ge precursor is a germaniumalkoxide, for example Ge(OEt)₄ or Ge(OMe)₄. In some embodiments, the Geprecursor is TDMAGe. In some embodiments, the Ge precursor includesalkyl and/or alkylamine groups. In some embodiments the Ge-precursor isnot a halide. In some embodiments the Ge-precursor may comprise ahalogen in at least one ligand, but not in all ligands. The germaniumprecursor may be provided with the aid of an inert carrier gas, such asargon.

In some embodiments the second reactant comprises a nitrogen-hydrogenbond. In some embodiments the second reactant is ammonia (NH₃). In someembodiments, the second reactant is molecular nitrogen. In someembodiments the second reactant is a nitrogen containing plasma. In someembodiments, the second reactant comprises an activated or excitednitrogen species. In some embodiments the second reactant may be aprovided in a nitrogen-containing gas pulse that can be a mixture ofnitrogen reactant and inactive gas, such as argon.

In some embodiments, a nitrogen-containing plasma is formed in areactor. In some embodiments, the plasma may be formed in situ on top ofthe substrate or in close proximity to the substrate. In otherembodiments, the plasma is formed upstream of the reaction chamber in aremote plasma generator and plasma products are directed to the reactionchamber to contact the substrate. As will be appreciated by the skilledartisan, in the case of remote plasma, the pathway to the substrate canbe optimized to maximize electrically neutral species and minimize ionsurvival before reaching the substrate.

Irrespective of the second reactant used, in some embodiments of thepresent disclosure, the use of a second reactant does not contributesignificant amounts of nitrogen to the deposited film. According to someembodiments, the resulting germanium film contains less than about 5-at%, less than about 2-at % or even less than about 1-at % nitrogen. Insome embodiments, the nitrogen content of the germanium film is lessthan about 0.5-at % or even less than about 0.2-at %.

In some embodiments hydrogen reactants are not used in the depositionprocess. In some embodiments, no elemental hydrogen (H₂) is provided inat least one deposition cycle, or in the entire deposition process. Insome embodiments, hydrogen plasma is not provided in at least onedeposition cycle or in the entire deposition process. In someembodiments, hydrogen atoms or radicals are not provided in at least onedeposition cycle, or in the entire deposition process.

In some embodiments the Ge precursor comprises at least one amine oralkylamine ligand, such as those presented in formulas (2) through (6)and (8) and (9), and the second reactant comprises NH₃.

Before starting the deposition of the film, the substrate is typicallyheated to a suitable growth temperature, as discussed above. Thepreferred deposition temperature may vary depending on a number offactors such as, and without limitation, the reactant precursors, thepressure, flow rate, the arrangement of the reactor, and the compositionof the substrate including the nature of the material to be depositedon. In some embodiments the deposition temperature is selected to bebetween the temperature where the germanium precursor does not decomposewithout the second precursor, at the lower end, and the temperaturewhere the precursor does decompose by itself, at the upper end. Asdiscussed elsewhere, in some embodiments the temperature may be lessthan about 600° C., less than about 450° C., less than about 400° C.,and in some cases, less than about 375° C. In some embodiments usingGe(OCH₂CH₃)₄ and NH₃ as the germanium and second reactants, thetemperature is about 350° C.

The processing time depends on the thickness of the layer to be producedand the growth rate of the film. In ALD, the growth rate of a thin filmis determined as thickness increase per one cycle. One cycle consists ofthe contacting and removing steps of the precursors and the duration ofone cycle is typically between about 0.2 seconds and about 30 seconds,more preferably between about 1 second and about 10 seconds, but it canbe on order of minutes or more in some cases, for example, where largesurface areas and volumes are present.

In some embodiments the growth rate of the germanium thin films may begreater than or equal to about 2 Å/cycle, greater than or equal to about5 Å/cycle, greater than or equal to about 10 Å/cycle, and, in someembodiments, even greater than about 15 Å/cycle.

In some embodiments the germanium film formed is a relatively puregermanium film. Preferably, aside from minor impurities no other metalor semi-metal elements are present in the film. In some embodiments thefilm comprises less than 1-at % of metal or semi-metal other than Ge. Insome embodiments, the germanium film comprises less than about 5-at % ofany impurity other than hydrogen, preferably less than about 3-at % ofany impurity other than hydrogen, and more preferably less than about1-at % of any impurity other than hydrogen. In some embodiments agermanium film comprises less than about 5 at-% nitrogen, less thanabout 3 at-% nitrogen less than about 2 at-% nitrogen or even less thanabout 1 at-% nitrogen. In some embodiments, a pure germanium filmcomprises less than about 2-at % oxygen, preferably less than about 1-at% or less than about 0.5-at % and even less than about 0.25-at %.

In some embodiments a germanium precursor comprising oxygen is utilizedand the germanium film comprises no oxygen or a small amount of oxygenas an impurity. In some embodiments the germanium film deposited using agermanium precursor comprising oxygen may comprise less than about 2at-% oxygen, less than about 1 at-%, less than about 0.5 at-% or evenless than about 0.25 at-%.

In some embodiments, the germanium film formed has step coverage of morethan about 50%, more than about 80%, more than about 90%, or even morethan about 95% on structures which have high aspect ratios. In someembodiments high aspect ratio structures have an aspect ratio that ismore than about 3:1 when comparing the depth or height to the width ofthe feature. In some embodiments the structures have an aspect ratio ofmore than about 5:1, or even an aspect ratio of 10:1 or greater.

Ge Precursors

A number of different Ge precursors can be used in the selectivedeposition processes. In some embodiments the Ge precursor istetravalent (i.e. Ge has an oxidation state of +IV). In someembodiments, the Ge precursor is not divalent (i.e., Ge has an oxidationstate of +II). In some embodiments, the Ge precursor may comprise atleast one alkoxide ligand. In some embodiments, the Ge precursor maycomprise at least one amine or alkylamine ligand. In some embodimentsthe Ge precursor is a metal-organic or organometallic compound. In someembodiments the Ge precursor comprises at least one halide ligand. Insome embodiments the Ge precursor does not comprise a halide ligand.

In some embodiments the Ge precursor comprises a Ge—O bond. In someembodiments the Ge precursor comprises a Ge—N bond. In some embodimentsthe Ge precursor comprises a Ge—C bond. In some embodiments the Geprecursor does not comprise Ge—H bond. In some embodiments the Geprecursor comprises equal or less than two Ge—H bonds per one Ge atom.

In some embodiments the Ge precursor is not solid at room temperature(e.g., about 20° C.).

For example, Ge precursors from formulas (1) through (9) below may beused in some embodiments.

GeOR₄  (1)

Wherein R is can be independently selected from the group consisting ofalkyl and substituted alkyl;

GeR_(x)A_(4-x)  (2)

Wherein the x is an integer from 1 to 4;

R is an organic ligand and can be independently selected from the groupconsisting of alkoxides, alkylsilyls, alkyl, substituted alkyl,alkylamines; and

A can be independently selected from the group consisting of alkyl,substituted alkyl, alkoxides, alkylsilyls, alkyl, alkylamines, halide,and hydrogen.

Ge(OR)_(x)A_(4-x)  (3)

Wherein the x is an integer from 1 to 4;

R can be independently selected from the group consisting of alkyl andsubstituted alkyl; and

A can be independently selected from the group consisting of alkyl,alkoxides, alkylsilyls, alkyl, substituted alkyl, alkylamines, halide,and hydrogen.

Ge(NR^(i)R^(II))₄  (4)

Wherein R^(I) can be independently selected from the group consisting ofhydrogen, alkyl and substituted alkyl; and

R^(II) can be independently selected from the group consisting of alkyland substituted alkyl;

Ge(NR^(I)R^(II))_(x)A_(4-x)  (5)

Wherein the x is an integer from 1 to 4;

R^(I) can be independently selected from the group consisting ofhydrogen, alkyl and substituted alkyl; and

R^(I) can be independently selected from the group consisting of alkyland substituted alkyl;

A can be independently selected from the group consisting of alkyl,alkoxides, alkylsilyls, alkyl, substituted alkyl, alkylamines, halide,and hydrogen.

Ge_(n)(NR^(I)R^(II))_(2n+2)  (6)

Wherein the n is an integer from 1 to 3;

R^(I) can be independently selected from the group consisting ofhydrogen, alkyl and substituted alkyl; and

R^(II) can be independently selected from the group consisting of alkyland substituted alkyl;

Ge_(n)(OR)_(2n+2)  (7)

Wherein the n is an integer from 1 to 3; and

Wherein R can be independently selected from the group consisting ofalkyl and substituted alkyl;

Ge_(n)R_(2n+2)  (8)

Wherein the n is an integer from 1 to 3; and

R is an organic ligand and can be independently selected from the groupconsisting of alkoxides, alkylsilyls, alkyl, substituted alkyl,alkylamines.

A_(3-x)R_(x)Ge—GeR_(y)A_(3-y)  (9)

Wherein the x is an integer from 1 to 3;

y is an integer from 1 to 3;

R is an organic ligand and can be independently selected from the groupconsisting of alkoxides, alkylsilyls, alkyl, substituted alkyl,alkylamines; and

A can be independently selected from the group consisting of alkyl,alkoxides, alkylsilyls, alkyl, substituted alkyl, alkylamines, halide,and hydrogen.

Preferred options for R include, but are not limited to, methyl, ethyl,propyl, isopropyl, n-butyl, isobutyl, tertbutyl for all formulas, morepreferred in ethyl and methyl. In some embodiments, the preferredoptions for R include, but are not limited to, C₃-C₁₀ alkyls, alkenyls,and alkynyls and substituted versions of those, more preferably C₃-C₆alkyls, alkenyls, and alkenyls and substituted versions of those.

In some embodiments the Ge precursor comprises one or more halides. Forexample, the precursor may comprise 1, 2, or 3 halide ligands. However,as mentioned above, in some embodiments the Ge precursor does notcomprise a halide.

In some embodiments a germane (GeH_(x)) is not used. In some embodimentsa compound comprising Ge and hydrogen may be used. In some embodiments agermane may be used, including, but not limited to, one or more of GeH₄and Ge₂H₆.

In some embodiments alkoxide Ge precursors may be used, including, butnot limited to, one or more of Ge(OMe)₄, Ge(OEt)₄, Ge(O^(i)Pr)₄,Ge(O^(n)Pr)₄ and Ge(O^(t)Bu)₄. In some embodiments the Ge precursor isTDMAGe. In some embodiments the Ge precursor is TDEAGe. In someembodiments the Ge precursor is TEMAGe.

Selective Deposition of Ru and Other Noble Metals on Metal

In some embodiments noble metal, preferably Ru metal, is selectivelydeposited on a first metal surface of a substrate, such as a Cu, Ni, Co,Al, W, Ru, or other noble metal, relative to a second, non-metal surfaceof the same substrate. In some embodiments noble metal may comprise oneof Au, Pt, Ir, Pd, Os, Ag, Hg, Po, Rh, Ru, Cu, Bi, Tc, Re, and Sb,preferably Ru.

In some embodiments noble metal is selectively deposited on a firstmetal surface of a substrate, such as a Cu, Ni, Co, Al, W, Ru, or othernoble metal surface, relative to a hydrophilic surface of the samesubstrate. In some embodiments the metal surface comprises an oxide suchas CuOx, NiOx, CoOx or RuOx or another noble metal oxide. In someembodiments a metal surface may no longer be conductive after it hasbeen treated. For example, a metal surface may be treated prior to or atthe beginning of the selective deposition process, such as by oxidation,and the treated surface may no longer be conductive. In some embodimentsan existing metal oxide surface may be treated prior to or at thebeginning of the selective deposition process, such as by reduction, andthe treated surface may then comprise metal.

In some embodiments noble metal is selectively deposited on a Cu surfacerelative to a second, different surface. In some embodiments noble metalis selectively deposited on a Ni surface relative to a second, differentsurface. In some embodiments noble metal is selectively deposited on aCo surface relative to a second, different surface. In some embodimentsnoble metal is selectively deposited on a Al surface relative to asecond, different surface. In some embodiments noble metal isselectively deposited on a W surface relative to a second, differentsurface. In some embodiments noble metal is selectively deposited on aRu surface relative to a second, different surface. In some embodimentsnoble metal is selectively deposited on a noble metal surface relativeto a second, different surface.

In some embodiments the second surface is a hydrophilic surface. In someembodiments the second, hydrophilic surface may comprise at least someOH-groups. In some embodiments the second surface is a —NH_(x)terminated surface. In some embodiments the second surface is a —SH_(x)terminated surface. In some embodiments the hydrophilic surface is adielectric surface. In some embodiments the hydrophilic surface maycomprise SiO₂, a low k material, or GeO₂.

For example, Ru bis(cyclopentadienyl) compounds can be highlynon-reactive toward hydrophilic oxide surfaces. The hydrophilic surfacemay comprise at least some OH-groups. In some embodiments thehydrophilic surface is a dielectric surface. In some embodiments thehydrophilic surface may comprise SiO₂, a low k material, or GeO₂. Insome embodiments noble metal, preferably Ru is selectively deposited bya cyclical deposition process. In some embodiments Ru or other noblemetal deposition on the first surface of the substrate relative to thesecond surface of the substrate is at least about 90% selective, atleast about 95% selective, at least about 96%, 97%, 98% or 99% orgreater selective. In some embodiments Ru or other noble metaldeposition only occurs on the first surface and does not occur on thesecond surface. In some embodiments Ru or other noble metal depositionon the first surface of the substrate relative to the second surface ofthe substrate is at least about 80% selective, which may be selectiveenough for some particular applications. In some embodiments depositionon the first surface of the substrate relative to the second surface ofthe substrate is at least about 50% selective, which may be selectiveenough for some particular applications.

In some embodiments the amount of impurities present in the selectivelydeposited noble metal film is low, which is essential when aiming athigh conductivity of the film. In some embodiments the amounts of H, Cand N impurities are typically in the order of 0.1 to 0.3 at-%. In someembodiments the amount of residual oxygen is typically in the range of0.3 to 0.5 at-%.

In some embodiments Ru is selectively deposited by a process such asthose described in U.S. Pat. No. 6,824,816, issued Nov. 30, 2002(attorney docket number SEPP16.001AUS), the entire disclosure of whichis attached hereto in the Appendix and hereby incorporated herein byreference.

In some embodiments Ru or another noble metal is deposited by a processsuch as those described in U.S. Pat. No. 7,666,773, issued Feb. 23, 2010(attorney docket number ASMMC.063AUS), or as described in U.S. Pat. No.8,025,922, issued Sep. 27, 2011 (attorney docket number ASMMC.068AUS),the entire disclosure of each of which is attached hereto in theAppendix and hereby incorporated herein by reference.

In some embodiments a noble metal is selectively deposited on a firstsurface of a substrate relative to a second, different surface of thesubstrate by an ALD type process comprising alternately and sequentiallycontacting the substrate with a first noble metal precursor and a secondreactant.

In some embodiments a substrate comprising a first surface and a secondsurface is provided and a noble metal is selectively deposited on afirst surface of a substrate by n ALD type deposition process comprisingmultiple cycles, each cycle comprising:

contacting the surface of a substrate with a vaporized first noble metalprecursor;

removing excess noble metal precursor and reaction byproducts, if any,from the surface;

contacting the surface of the substrate with a second vaporizedreactant;

removing from the surface excess second reactant and any gaseousby-products formed in the reaction between the noble metal precursor lawon the first surface of the substrate and the second reactant, and;

repeating the contacting and removing steps until a noble metal thinfilm of the desired thickness has been formed.

As mentioned above, in some embodiments one or more surfaces of thesubstrate may be treated in order to enhance deposition on one surfacerelative to one or more different surfaces prior to beginning thedeposition process. In some embodiments the first, metal surface can betreated to enhance deposition on the first surface relative to thesecond, non-metal surface. In some embodiments the first, metal surfacecan be activated, such as by surface modification. In some embodimentsthe second, non-metal surface can be treated to provide an OH-terminatedsurface, or can be deactivated, such as by passivation, prior todeposition of noble metal.

In some embodiments an existing metal oxide surface may be treated priorto or at the beginning of the selective deposition process, such as byreduction, and the treated surface may then comprise metal. In someembodiments the first surface comprising a metal oxide, for example CuO,may be exposed to a reducing agent. In some embodiments the reducingagent may comprise an organic compound. In some embodiments the reducingagent may comprise an organic compound containing at least onefunctional group selected from —OH, —CHO, and —COOH. In someembodiments, after pretreatment a first surface may no longer comprise ametal oxide, for example CuO, and may comprise a conductive metalsurface, for example Cu. In some embodiments the first, metal surface,for example a W surface, is activated by, for example, treatment to formSi—H surface terminations thereon. In some embodiments activation of thefirst surface may comprise contacting the first surface with a chemicalthat provides Si-H surface terminations. In some embodiments activationof the first surface may comprise exposing the substrate to disilane toform Si—H surface terminations on the first surface.

In some embodiments the second, non-metal surface is deactivated, suchas by a treatment to provide a surface on which metal deposition isinhibited. In some embodiments deactivation may comprise treatment witha passivation chemical. In some embodiments the deactivation treatmentcan occur prior to the deposition of a metal on a first metal surface.In some embodiments the deactivation treatment may be an in situdeactivation treatment. In some embodiments deactivation of thehydrophilic surface may comprise replacing at least OH-groups with othergroups. In some embodiments deactivation can include treatment toincrease the amount of OH-groups on the second, non-metal, surface.

In some embodiments a dielectric surface can be passivated to inhibitdeposition of a metal thereon. For example, the dielectric surface maybe contacted with a chemical that provides a silylated (—Si—(CH₃)— or—Si(CH₃)₃) surface or a halogenated surface or a —SiH₃ surface. In someembodiments the dielectric surface is chlorinated or fluorinated, suchas a Si—Cl surface. A halogenated surface can be achieved by treatingthe surface with a halide chemical, such as CCl₄ or a metal halide,which is capable of forming volatile metal oxyhalides, such as WF₆,NbF₅, or NbCl₅, and leaving the halide, such as the chloride or fluorideon the surface. The passivation can be used to inhibit deposition of ametal on a dielectric surface relative to a metal surface. In someembodiments the passivation chemical is one or more oftrimethylchlorosilane (CH₃)₃SiCl (TMCS), trimethyldimethylaminosilane(CH₃)₃SiN(CH₃)₂ or another type of alkyl substituted silane havingformula R_(4-x)SiX_(x), wherein x is from 1 to 3 and each R canindependently selected to be a C1-C5 hydrocarbon, such as methyl, ethyl,propyl or butyl, preferably methyl, and X is halide or X is anothergroup capable of reacting with OH-groups, such as an alkylamino group—NR1R2, wherein each R1 can be independently selected to be hydrogen orC1-C5 hydrocarbon, preferably methyl or ethyl, R2 can be independentlyselected to be C1-C5 hydrocarbon, preferably methyl or ethyl, preferablyX is chloride or dimethylamino. In some embodiments the passivationchemical can be a silane compound comprising at least one alkylaminogroup, such as bis(diethylamino)silane, or a silane compound comprisinga SiH₃ group, or silazane, such hexamethyldisilazane (HMDS).

Although the illustrated noble metal deposition cycle begins withcontacting the substrate with the first noble metal precursor, in otherembodiments the deposition cycle begins with contacting the substratewith the second reactant. It will be understood by the skilled artisanthat contacting the substrate surface with the first noble metalprecursor and second reactant are interchangeable in the ALD cycle.

When the noble metal precursor contacts the substrate, the noble metalprecursor may form at least a monolayer, less than a monolayer, or morethan a monolayer.

In some embodiments, a carrier gas is flowed continuously to a reactionspace throughout the deposition process. In some embodiments in eachdeposition cycle the first germanium precursor is pulsed into a reactionchamber. In some embodiments excess noble metal precursor is thenremoved from the reaction chamber. In some embodiments, the carrier gascomprises nitrogen. In some embodiments a separate purge gas isutilized.

In some embodiments, the reactants and reaction by-products can beremoved from the substrate surface by stopping the flow of secondreactant while continuing the flow of an inert carrier gas. In someembodiments the substrate is moved such that different reactantsalternately and sequentially contact the surface of the substrate in adesired sequence for a desired time. In some embodiments the removingsteps are not performed. In some embodiments no reactant may be removedfrom the various parts of a chamber. In some embodiments the substrateis moved from a part of the chamber containing a first precursor toanother part of the chamber containing the second reactant. In someembodiments the substrate is moved from a first reaction chamber to asecond, different reaction chamber.

A noble metal precursor employed in the ALD type processes may be solid,liquid, or gaseous material under standard conditions (room temperatureand atmospheric pressure), provided that a noble metal precursor is invapor phase before it is contacted with the substrate surface.

Contacting a substrate surface with a vaporized precursor means that theprecursor vapor is in contact with the substrate surface for a limitedperiod of time. Typically, the contacting time is from about 0.05 to 10seconds. However, depending on the substrate type and its surface area,the contacting time may be even higher than 10 seconds. Contacting timescan be on the order of minutes in some cases. The optimum contactingtime can be determined by the skilled artisan based on the particularcircumstances. In some embodiments the substrate is moved such thatdifferent reactants alternately and sequentially contact the surface ofthe substrate in a desired sequence for a desired time. In someembodiments the substrate is moved from a first reaction chamber to asecond, different reaction chamber. In some embodiments the substrate ismoved within a first reaction chamber.

In some embodiments “contacting” a substrate with a vaporized precursormay comprise the precursor vapor being conducted a the chamber for alimited period of time. Typically, the contacting time is from about0.05 to 10 seconds. However, depending on the substrate type and itssurface area, the contacting time may be even higher than 10 seconds.Preferably, for a 300 mm wafer in a single wafer ALD reactor, thesubstrate is contacted by noble metal precursor for from 0.05 to 10seconds, more preferably for from 0.5 to 3 seconds and most preferablyfor about 0.5 to 1.0 seconds. In some embodiments the substrate iscontacted by the second reactant for from about 0.05 to 10 seconds, morepreferably for from 1 to 5 seconds, most preferably about for from 2 to3 seconds. Contacting times can be on the order of minutes in somecases. The optimum contacting time can be readily determined by theskilled artisan based on the particular circumstances.

The mass flow rate of the noble metal precursor can be determined by theskilled artisan. In one embodiment, for deposition on 300 mm wafers theflow rate of noble metal precursor is preferably between about 1 and1000 sccm without limitation, more preferably between about 100 and 500sccm. The mass flow rate of the noble metal precursor is usually lowerthan the mass flow rate of oxygen, which is usually between about 10 and10000 sccm without limitation, more preferably between about 100-2000sccm and most preferably between 100-1000 sccm.

In some embodiments removing reaction byproducts can comprise evacuatingthe chamber with a vacuum pump and/or by replacing the gas inside thereactor with an inert gas such as argon or nitrogen. Typical removaltimes are from about 0.05 to 20 seconds, more preferably between about 1and 10, and still more preferably between about 1 and 2 seconds.

In some embodiments before starting the deposition of the film, thesubstrate is typically heated to a suitable growth temperature. In someembodiments, the growth temperature of the noble metal thin film isbetween about 150° C. and about 450° C., more preferably between about200° C. and about 400° C. In some embodiments the preferred depositiontemperature may vary depending on a number of factors such as, andwithout limitation, the reactant precursors, the pressure, flow rate,the arrangement of the reactor, and the composition of the substrateincluding the nature of the material to be deposited on and the natureof the material on which deposition is to be avoided. The specificgrowth temperature may be selected by the skilled artisan using routineexperimentation in view of the present disclosure to maximize theselectivity of the process.

The processing time depends on the thickness of the layer to be producedand the growth rate of the film. In ALD, the growth rate of a thin filmis determined as thickness increase per one cycle. One cycle consists ofthe pulsing and purging steps of the precursors and the duration of onecycle is typically between about 0.2 and 30 seconds, more preferablybetween about 1 and 10 seconds, but it can be on order of minutes ormore in some cases.

In some embodiments the noble metal thin film comprises multiplemonolayers of a single noble metal. However, in some embodiments, thefinal metal structure may comprise noble metal compounds or alloyscomprising two or more different noble metals. For example, the growthcan be started with the deposition of platinum and ended with thedeposition of ruthenium metal. Noble metals are preferably selected fromthe group consisting of Pt, Au, Ru, Rh, Ir, Pd and Ag.

Noble metals are well known in the art and include, for example, Ru, Rh,Pd, Ag, Re, Os, Ir, and Pt. Suitable noble metal precursors may beselected by the skilled artisan. In general, metal compounds where themetal is bound or coordinated to oxygen, nitrogen, carbon or acombination thereof are preferred. In some embodiments metallocenecompounds, beta diketonate compounds and acetamidinato compounds areused.

In some embodiments noble metal precursors are cyclopentadienyl andacetylacetonate (acac) precursor compounds. In some embodiments abis(ethylcyclopentadienyl) noble metal compound is used.

In some embodiments a noble metal precursor may be selected from thegroup consisting of bis(cyclopentadienyl)ruthenium, tris(2,2,6,6tetramethyl 3,5-heptanedionato)ruthenium andtris(N,N′-diisopropylacetamidinato)ruthenium(III) and their derivatives,such as bis(N,N′-diisopropylacetamidinato)ruthenium(II) dicarbonyl,bis(ethylcyclopentadienyl)ruthenium,bis(pentamethylcyclopentadienyl)ruthenium and bis(2,2,6,6 tetramethyl3,5-heptanedionato)(1,5 cyclooctadiene)ruthenium(II). In someembodiments, the precursor is bis(ethylcyclopentadienyl) ruthenium(Ru(EtCp)2).

In some embodiments noble metal precursors can include(trimethyl)methylcyclopentadienylplatinum(IV), platinum (II)acetylacetonato, bis(2,2,6,6 tetramethyl 3,5 heptanedionato)platinum(II)and their derivatives.

In some embodiments noble metal precursors can includetris(acetylacetonato)iridium(III) and derivatives thereof

In some embodiments noble metal precursors can includebis(hexafluoroacetylacetonate)palladium(II) and derivatives thereof

In some embodiments the second reactant comprises an oxygen containingreactant. In some embodiments the second reactant can comprise oxygen ora mixture of oxygen and another gas. In some embodiments the secondreactant may comprises diatomic oxygen, or a mixture of diatomic oxygenand another gas. In some embodiments the second reactant may comprise anoxygen containing compound, such as H₂O₂, N₂O and/or an organicperoxide. In some embodiments a second reactant may form oxygen inside areaction chamber, for example by decomposing oxygen containingcompounds. In some embodiments a second reactant may comprisecatalytically formed oxygen. In some embodiments the catalyticalformation of a second reactant comprising oxygen may include conductinga vaporized aqueous solution of H₂O₂ over a catalytic surface, forexample platinum or palladium. In some embodiments a catalytic surfacemay be located inside a reaction chamber. In some embodiments acatalytic surface may not be located inside the reaction chamber.

In some embodiments the second reactant comprises free-oxygen or ozone,more preferably molecular oxygen. The second reactant is preferably puremolecular diatomic oxygen, but can also be a mixture of oxygen andinactive gas, for example, nitrogen or argon.

In some embodiments the second reactant preferably comprises afree-oxygen containing gas, more preferably a molecularoxygen-containing gas, and can therefore consist of a mixture of oxygenand inactive gas, for example, nitrogen or argon. In some embodimentspreferred oxygen content of the second reactant is from about 10 to 25%.In some embodiments one preferred source of oxygen is air. In the caseof relatively small substrates (e.g., up to 4 inch wafers) the mass flowrate of the second reactant may preferably between about 1 and 25 sccm,more preferably between about 1 and 8 sccm. In case of larger substratesthe mass flow rate of the second reactant gas may be scaled up as isunderstood by one of skill in the art.

Examples of suitable arrangements of reactors used for the deposition ofthin films according to the processes disclosed herein are, forinstance, commercially available ALD equipment, such as the F-120 andPulsar™ reactors, produced by ASM Microchemistry Ltd. In addition tothese ALD reactors, many other kinds of reactors capable for ALD growthof thin films, including CVD reactors equipped with appropriateequipment and means for pulsing the precursors, can be employed forcarrying out the processes disclosed herein. In some embodiments thegrowth processes can optionally be carried out in a cluster tool, wherethe substrate arrives from a previous process step, the metal film isproduced on the substrate, and then the substrate is transported to thefollowing process step. In a cluster tool, the temperature of thereaction space can be kept constant, which clearly improves thethroughput compared to a reactor in which is the substrate is heated upto the process temperature before each run.

Selective Deposition of W on Metal

In some embodiments W is selectively deposited on a metal surface, suchas Ni, Co, Cu, Al, W, Ru, or other noble metal relative to a hydrophilicsurface of the same substrate, such as a passivated surface. In someembodiments W is selectively deposited on a Cu surface, relative to asecond, different surface. In some embodiments W is selectivelydeposited on a Ni surface, relative to a second, different surface. Insome embodiments W is selectively deposited on a Co surface, relative toa second, different surface. In some embodiments W is selectivelydeposited on a Al surface, relative to a second, different surface. Insome embodiments W is selectively deposited on a Ru surface, relative toa second, different surface. In some embodiments W is selectivelydeposited on a noble metal surface, relative to a second, differentsurface.

In some embodiments W deposition on the first surface of the substraterelative to the second surface of the substrate is at least about 90%selective, at least about 95% selective, at least about 96%, 97%, 98% or99% or greater selective. In some embodiments W deposition only occurson the first surface and does not occur on the second surface. In someembodiments W deposition on the first surface of the substrate relativeto the second surface of the substrate is at least about 80% selective,which may be selective enough for some particular applications. In someembodiments deposition on the first surface of the substrate relative tothe second surface of the substrate is at least about 50% selective,which may be selective enough for some particular applications.

In some embodiments the second surface is a hydrophilic surface. In someembodiments the hydrophilic surface may comprise at least someOH-groups. In some embodiments the second surface is a —NHx terminatedsurface. In some embodiments the second surface is a —SHx terminatedsurface. In some embodiments the hydrophilic surface is a dielectricsurface. In some embodiments the hydrophilic surface may comprise SiO₂,a low k material, or GeO₂.

As previously discussed, in some embodiments the second surface istreated to facilitate selective deposition of W on a metal surfacerelative to the second surface. For example, the second surface may betreated to provide a hydrophilic OH-terminated surface. In someembodiments a hydrophilic OH-terminated surface may be treated toincrease the amount of OH-groups on the surface. For example, thedielectric surface may be exposed to H₂O vapor in order to increase thenumber of OH-groups at the surface. Another example includes exposing adielectric surface to a carrier gas that has flowed through a bubbler ata temperature of between 25° C. and 40° C. In some embodiments thedielectric surface is exposed to air in order to provide a hydrophilicsurface that comprises at least some OH-groups. In some embodiments ahydrophilic surface is not treated prior to deposition.

In some embodiments a dielectric surface can be passivated to inhibitdeposition of a metal thereon. For example, the dielectric surface maybe contacted with a chemical that provides a silylated (—Si—(CH₃)— or—Si(CH₃)₃) surface or a halogenated surface or a —SiH₃ surface. In someembodiments the dielectric surface is chlorinated or fluorinated, suchas a Si—Cl surface. A halogenated surface can be achieved by treatingthe surface with a halide chemical, such as CCl₄ or a metal halide,which is capable of forming volatile metal oxyhalides, such as WF₆,NbF₅, or NbCl₅, and leaving the halide, such as the chloride or fluorideon the surface. The passivation can be used to inhibit deposition of ametal on a dielectric surface relative to a metal surface. In someembodiments the passivation chemical is one or more oftrimethylchlorosilane (CH₃)₃SiCl (TMCS), trimethyldimethylaminosilane(CH₃)₃SiN(CH₃)₂ or another type of alkyl substituted silane havingformula R_(4-x)SiX_(x), wherein x is from 1 to 3 and each R canindependently selected to be a C1-C5 hydrocarbon, such as methyl, ethyl,propyl or butyl, preferably methyl, and X is halide or X is anothergroup capable of reacting with OH-groups, such as an alkylamino group—NR1R2, wherein each R1 can be independently selected to be hydrogen orC1-C5 hydrocarbon, preferably methyl or ethyl, R2 can be independentlyselected to be C1-C5 hydrocarbon, preferably methyl or ethyl, preferablyX is chloride or dimethylamino. In some embodiments the passivationchemical can be a silane compound comprising at least one alkylaminogroup, such as bis(diethylamino)silane, or a silane compound comprisinga SiH₃ group, or silazane, such hexamethyldisilazane (HMDS). Forexample, in some embodiments the hydrophilic surface may be contactedwith a chemical that provides an H-terminated surface. In someembodiments a hydrophilic surface is passivated against W deposition byforming a layer of Sb on the hydrophilic surface according to methodspreviously discussed in the present disclosure.

In some embodiments W is selectively deposited by a cyclical depositionprocess.

In some embodiments W is selectively deposited by a process such as thatdescribed in US Publication No. 2013/0196502, published Aug. 1, 2013(attorney docket number ASMMC.098AUS), the disclosure of which is herebyincorporated in its entirety.

In some embodiments the methods comprise selectively depositing W on asubstrate comprising a first metal surface and a second hydrophilicsurface using a plurality of deposition cycles. The cycle comprises:contacting the substrate with a first precursor comprising silicon orboron to selectively form a layer of first material comprising Si or Bover the first metal surface relative to the second dielectric surface;and converting the first material to a second metallic material byexposing the substrate to a second precursor comprising metal.

In some embodiments a substrate comprising a first surface and a secondsurface is provided and a metal, here W, is selectively deposited on afirst surface of a substrate by a cyclical deposition process comprisingmultiple cycles, each cycle comprising:

contacting the surface of a substrate with a vaporized first precursor,for example comprising Si or B;

removing excess first precursor and reaction by products, if any, fromthe surface;

contacting the surface of the substrate with a second vaporizedprecursor, for example WF₆;

removing from the surface excess second precursor and any gaseousby-products formed in the reaction between the first precursor layer onthe first surface of the substrate and the second precursor, and;

repeating the contacting and removing steps until a metal, here W, thinfilm of the desired thickness has been formed.

As mentioned above, in some embodiments one or more surfaces of thesubstrate may be treated in order to enhance deposition on one surfacerelative to one or more different surfaces prior to beginning thedeposition process. In some embodiments the second, non-metal surfacecan be treated to provide an OH-terminated surface, or can bedeactivated, such as by passivation, prior to deposition of the metal,here W.

Although the illustrated W deposition cycle begins with contacting thesubstrate with the first W precursor, in other embodiments thedeposition cycle begins with contacting the substrate with the secondreactant. It will be understood by the skilled artisan that contactingthe substrate surface with the first W precursor and second reactant areinterchangeable in the deposition cycle.

First Precursors

In some embodiments a first precursor is provided to the substrate suchthat a layer is selectively formed on a first metal surface of thesubstrate relative to a second different surface of the substrate. Insome embodiments the first precursor preferably comprises silicon orboron. In some embodiments a 0.05-4 nm thick layer of Si or B is formedon the first surface of the substrate. In some embodiments a 0.1-2 nmthick layer of Si or B is formed on the first surface of the substrate.In some embodiments less than 1 nm of Si or B can be used. Without beingbound to a theory, it is believed that the first metal surface on thesubstrate can catalyze or assist in the adsorption or decomposition ofthe first precursor in comparison to the reactivity of the secondsurface or insulator. In some embodiments the formation of silicon orboron on the first surface is self-limiting, such that up to a monolayeris formed upon exposure to the reactant. In some embodiments the siliconor boron source chemical can decompose on the first surface.

In some embodiments, the silicon source chemical is selected from thesilane family Si_(n)H_(2n+2) (n is equal to or greater than 1) or thecyclic silane family Si_(n)H_(2n) (n is equal to or greater than 3). Insome embodiments the silicon source comprises silane or disilane. Mostpreferably the silane is disilane Si₂H₆ or trisilane Si₃H₈. In someembodiments the silicon source can be selected from silane compoundshaving the formula: SiH_(x)L_(y), where L is a ligand selected from thegroups including: alkyl, alkenyl, alkynyl, alkoxide, and amine. In somecases L is a ligand selected from the halide group: F, Cl, Br and I.

In some embodiments the first precursor comprises boron. In someembodiments the first precursor is diborane (B₂H₆). Diborane has similarproperties to some of the silane based compounds. For example, diboranehas a lower decomposition temperature than disilane but similar thermalstability to trisilane (silcore).

Other precursors comprising boron could also be used. The availabilityof a vast number of boron compounds makes it possible to choose one withthe desired properties. In addition, it is possible to use more than oneboron compound. Preferably, one or more of the following boron compoundsis used:

Boranes according to formula I or formula II.

B_(n)H_(n+x),  (I)

Wherein n is an integer from 1 to 10, preferably from 2 to 6, and x isan even integer, preferably 4, 6 or 8.

B_(n)H_(m)  (II)

Wherein n is an integer from 1 to 10, preferably form 2 to 6, and m isan integer different than n, from 1 to 10, preferably from 2 to 6.

Of the above boranes according to formula I, examples includenido-boranes (B_(n)H_(n+4)), arachno-boranes (B_(n)H_(n+6)) andhyph-boranes (B_(n)H_(n+8)). Of the boranes according to formula II,examples include conjuncto-boranes (B_(n)H_(m)). Also, borane complexessuch as (CH₃CH₂)₃N—BH₃ can be used.

Borane halides, particularly fluorides, bromides and chlorides. Anexample of a suitable compound is B₂H₅Br. Further examples compriseboron halides with a high boron/halide ratio, such as B₂F₄, B₂Cl₄ andB₂Br₄. It is also possible to use borane halide complexes.

Halogenoboranes according to formula III.

B_(n)X_(n)  (III)

Wherein X is Cl or Br and n is 4 or an integer from 8 to 12 when X isC1, or n is an integer from 7 to 10 when X is Br.

Carboranes according to formula IV.

C₂B_(n)H_(n+x)  (IV)

Wherein n is an integer from 1 to 10, preferably from 2 to 6, and x isan even integer, preferably 2, 4 or 6.

Examples of carboranes according to formula IV include closo-carboranes(C₂B_(n)H_(n+2)), nido-carboranes (C₂B_(n)H_(n+4)) andarachno-carboranes (C₂B_(n)H_(n+6)).

Amine-borane adducts according to formula V.

R₃NBX₃  (V)

Wherein R is linear or branched C1 to C10, preferably C1 to C4 alkyl orH, and X is linear or branched C1 to C10, preferably C1 to C4 alkyl, Hor halogen.

Aminoboranes where one or more of the substituents on B is an aminogroup according to formula VI.

R₂N  (VI)

Wherein R is linear or branched C1 to C10, preferably C1 to C4 alkyl orsubstituted or unsubstituted aryl group.

An example of a suitable aminoborane is (CH₃)₂NB(CH₃)₂.

Cyclic borazine (—BH—NH—)₃ and its volatile derivatives.

Alkyl borons or alkyl boranes, wherein the alkyl is typically linear orbranched C1 to C10 alkyl, preferably C2 to C4 alkyl.

In some embodiments the first precursor comprises germanium. In someembodiments, the germanium source chemical is selected from the germanefamily Ge_(n)H₂₊₂ (n is equal to or greater than 1) or the cyclicgermane family Ge_(n)H_(2n) (n is equal to or greater than 3). In somepreferred embodiments the germanium source comprises germane GeH₄. Insome embodiments the germanium source can be selected from germanecompounds having the formula: GeH_(x)L_(y), where L is a ligand selectedfrom the groups including: alkyl, alkenyl, alkynyl, alkoxide, and amine.In some cases L is a ligand selected from the halide group: F, Cl, Brand I.

W Precursors

In some embodiments the second precursor preferably comprises W. In someembodiments the second precursor comprises a W halide (F, Cl, Br, I). Insome embodiments the second precursor preferably comprises fluorine. Insome embodiments, the second precursor comprises WF₆.

Selective Deposition of Al on Metal

In some embodiments Al is selectively deposited on a metal surface, suchas Ni, Co, Cu, Al, W, Ru, or other noble metal relative to a hydrophilicsurface of the same substrate, such as a passivated surface. In someembodiments Al is selectively deposited on a Cu surface, relative to asecond, different surface. In some embodiments Al is selectivelydeposited on a Ni surface, relative to a second, different-surface. Insome embodiments Al is selectively deposited on a Co surface, relativeto a second, different surface. In some embodiments Al is selectivelydeposited on a Al surface, relative to a second, different surface. Insome embodiments Al is selectively deposited on a Ru surface, relativeto a second, different surface. In some embodiments Al is selectivelydeposited on a noble metal surface, relative to a second, differentsurface.

In some embodiments Al deposition on the first surface of the substraterelative to the second surface of the substrate is at least about 90%selective, at least about 95% selective, at least about 96%, 97%, 98% or99% or greater selective. In some embodiments Al deposition only occurson the first surface and does not occur on the second surface. In someembodiments Al deposition on the first surface of the substrate relativeto the second surface of the substrate is at least about 80% selective,which may be selective enough for some particular applications. In someembodiments deposition on the first surface of the substrate relative tothe second surface of the substrate is at least about 50% selective,which may be selective enough for some particular applications.

In some embodiments the second surface is a hydrophilic surface. In someembodiments the hydrophilic surface may comprise at least someOH-groups. In some embodiments the second surface is a —NHx terminatedsurface. In some embodiments the second surface is a —SHx terminatedsurface. In some embodiments the hydrophilic surface is a dielectricsurface. In some embodiments the hydrophilic surface may comprise SiO₂,a low k material, or GeO₂.

As previously discussed, in some embodiments the second surface istreated to facilitate selective deposition of Al on a metal surfacerelative to the second surface. For example, the second surface may betreated to provide a hydrophilic OH-terminated surface. In someembodiments a hydrophilic OH-terminated surface may be treated toincrease the amount of OH-groups on the surface. For example, thedielectric surface may be exposed to H₂O vapor in order to increase thenumber of OH-groups at the surface. Another example includes exposing adielectric surface to a carrier gas that has flowed through a bubbler ata temperature of between 25° C. and 40° C. In some embodiments thedielectric surface is exposed to air in order to provide a hydrophilicsurface that comprises at least some OH-groups. In some embodiments ahydrophilic surface is not treated prior to deposition.

In some embodiments the hydrophilic surface is deactivated, such as bypassivation prior to deposition of Al. In some embodiments deactivationof the hydrophilic surface may comprise replacing at least OH-groupswith other groups. In some embodiments the hydrophilic dielectricsurface is treated with a passivation chemical to form a passivatedsurface. For example, the hydrophilic surface may be silylated orhalogenated, such as chlorinated or fluorinated, prior to deposition ofthe Al. In some embodiments the hydrophilic surface may be treated toform a silylated surface, such as a silylated —Si—(CH₃)x or —Si(CH₃)₃surface. In some embodiments the hydrophilic surface may be treated toform a halogenated surface, such as a chlorinated or fluorinatedsurface. For example, the halogenated surface may be a Si—Cl surface. Insome embodiments the hydrophilic surface may be treated to provide aH-terminated surface, for example a —SiH₃ surface. For example, in someembodiments the hydrophilic surface may be contacted with a chemicalthat provides an H-terminated surface.

As noted above, processes described herein enable use of ALD typedeposition techniques to selectively deposit Al. The ALD type depositionprocess is mostly surface-controlled (based on controlled reactions atthe first substrate surface) and thus has the advantage of providinghigh conformality at relatively low temperatures. However, in someembodiments, the Al precursor may at least partially decompose.Accordingly, in some embodiments the ALD type process described hereinis a pure ALD process in which no decomposition of precursors isobserved. In other embodiments reaction conditions, such as reactiontemperature, are selected such that a pure ALD process is achieved andno precursor decomposition takes place.

In some embodiments Al is selectively deposited by a vapor depositionprocess. In some embodiments an aluminum precursor comprising an Al—Hcompound is used. In some embodiments Al is selectively deposited by aprocess such as that described in The Chemistry of Metal CVD, edited byToivo Kodas and Mark Hampden-Smith, Weinheim; VCH, 1994, ISBN3-527-29071-0, section 2.6.6, pp. 57 and 83, the disclosure of which isincorporated herein in its entirety. Other methods of vapor depositionof Al are known in the art and can be adapted to selectively deposit Alon a first metal surface relative to a second, different surface.

In some embodiments Al is selectively deposited by a vapor depositionprocess. In some embodiments Al is selectively deposited by a cyclicaldeposition process. In some embodiments Al is selectively deposited on afirst surface of a substrate relative to a second, different surface ofthe substrate by an ALD type process comprising alternately andsequentially contacting the substrate with a first Al precursor and asecond reactant.

In some embodiments a substrate comprising a first surface and a secondsurface is provided and a metal, here Al, is selectively deposited on afirst surface of a substrate by a cyclical deposition process comprisingmultiple cycles, each cycle comprising:

contacting the surface of a substrate with a vaporized first metalprecursor, for example DMAH or DMEAA;

removing excess metal precursor and reaction by products, if any, fromthe surface;

contacting the surface of the substrate with a second vaporizedreactant, for example H₂;

removing from the surface excess second reactant and any gaseousby-products formed in the reaction between the metal precursor layer onthe first surface of the substrate and the second reactant, and;

repeating the contacting and removing steps until a metal, here Al, thinfilm of the desired thickness has been formed.

As mentioned above, in some embodiments one or more surfaces of thesubstrate may be treated in order to enhance deposition on one surfacerelative to one or more different surfaces prior to beginning thedeposition process. In some embodiments the second, non-metal surfacecan be treated to provide an OH-terminated surface, or can bedeactivated, such as by passivation, prior to deposition of the metal,here Al.

Although the illustrated Al deposition cycle begins with contacting thesubstrate with the first Al precursor, in other embodiments thedeposition cycle begins with contacting the substrate with the secondreactant. It will be understood by the skilled artisan that contactingthe substrate surface with the first Al precursor and second reactantare interchangeable in the deposition cycle.

When the Al precursor contacts the substrate, the Al precursor may format least a monolayer, less than a monolayer, or more than a monolayer.

In some embodiments the Al precursor comprises an Al—H compound. In someembodiments the Al precursor comprises an alane. In some embodiments theAl precursor comprises at least one of trimethylamine alane (TMAA),trimethylamine alane (TEAA), and dimethylethylamine alane (DMEAA). Insome embodiments the Al precursor is selected from trimethylaluminum(TMA), triethylaluminum (TEA), triisobutylaluminum (TIBA),diethyaluminum chloride (DEACl), Dimethylaluminum hydride (DMAH),trimethylamine alane (TMAA), trimethylamine alane (TEAA),dimethylethylamine alane (DMEAA), and trimethylamine alumina borane(TMAAB). The Al precursor may be provided with the aid of an inertcarrier gas, such as argon.

In some embodiments the second reactant comprises hydrogen. In someembodiments the second reactant comprises hydrogen gas.

Selective Deposition of Cu on Metal

In some embodiments Cu is selectively deposited on a metal surface, suchas Ni, Co, Cu, Al, Ru, or other noble metal relative to a hydrophilicsurface of the same substrate, such as a passivated surface. In someembodiments Cu is selectively deposited on a Cu surface, relative to asecond, different surface. In some embodiments Cu is selectivelydeposited on a Ni surface, relative to a second, different-surface. Insome embodiments Cu is selectively deposited on a Co surface, relativeto a second, different surface. In some embodiments Cu is selectivelydeposited on a Al surface, relative to a second, different surface. Insome embodiments Cu is selectively deposited on a Ru surface, relativeto a second, different surface. In some embodiments Cu is selectivelydeposited on a noble metal surface, relative to a second, differentsurface.

In some embodiments Cu deposition on the first surface of the substraterelative to the second surface of the substrate is at least about 90%selective, at least about 95% selective, at least about 96%, 97%, 98% or99% or greater selective. In some embodiments Cu deposition only occurson the first surface and does not occur on the second surface. In someembodiments Cu deposition on the first surface of the substrate relativeto the second surface of the substrate is at least about 80% selective,which may be selective enough for some particular applications. In someembodiments deposition on the first surface of the substrate relative tothe second surface of the substrate is at least about 50% selective,which may be selective enough for some particular applications.

In some embodiments the second surface is a hydrophilic surface. In someembodiments the hydrophilic surface may comprise at least someOH-groups. In some embodiments the second surface is a —NH_(x)terminated surface. In some embodiments the second surface is a —SH_(x)terminated surface. In some embodiments the hydrophilic surface is adielectric surface. In some embodiments the hydrophilic surface maycomprise SiO₂, a low k material, or GeO₂.

As previously discussed, in some embodiments the second surface istreated to facilitate selective deposition of Cu on a metal surfacerelative to the second surface. For example, the second surface may betreated to provide a hydrophilic OH-terminated surface. In someembodiments a hydrophilic OH-terminated surface may be treated toincrease the amount of OH-groups on the surface. For example, thedielectric surface may be exposed to H₂O vapor in order to increase thenumber of OH-groups at the surface. Another example includes exposing adielectric surface to a carrier gas that has flowed through a bubbler ata temperature of between 25° C. and 40° C. In some embodiments thedielectric surface is exposed to air in order to provide a hydrophilicsurface that comprises at least some OH-groups. In some embodiments ahydrophilic surface is not treated prior to deposition.

In some embodiments the hydrophilic surface is deactivated, such as bypassivation prior to deposition of Cu. In some embodiments deactivationof the hydrophilic surface may comprise replacing at least OH-groupswith other groups. In some embodiments the hydrophilic dielectricsurface is treated with a passivation chemical to form a passivatedsurface. For example, the hydrophilic surface may be silylated orhalogenated, such as chlorinated or fluorinated, prior to deposition ofthe Cu. In some embodiments the hydrophilic surface may be treated toform a silylated surface, such as a silylated —Si—(CH₃)x or —Si(CH₃)₃surface. In some embodiments the hydrophilic surface may be treated toform a halogenated surface, such as a chlorinated or fluorinatedsurface. For example, the halogenated surface may be a Si—Cl surface. Insome embodiments the hydrophilic surface may be treated to provide aH-terminated surface, for example a —SiH₃ surface. For example, in someembodiments the hydrophilic surface may be contacted with a chemicalthat provides an H-terminated surface.

As noted above, processes described herein enable use of ALD typedeposition techniques to selectively deposit Cu. The ALD type depositionprocess is mostly surface-controlled (based on controlled reactions atthe first substrate surface) and thus has the advantage of providinghigh conformality at relatively low temperatures. However, in someembodiments, the Cu precursor may at least partially decompose.Accordingly, in some embodiments the ALD type process described hereinis a pure ALD process in which no decomposition of precursors isobserved. In other embodiments reaction conditions, such as reactiontemperature, are selected such that a pure ALD process is achieved andno precursor decomposition takes place.

In some embodiments Cu is selectively deposited by a cyclical depositionprocess. In some embodiments Cu can be selectively deposited bydecomposing Cu(I) N,N′-di-sec-butylacetamidinate [Cu(sec-Bu2-AMD)]2, asdisclosed in Booyong S Lim, Antti Rahtu, Roy G Gordon, Nature Materials,Vol. 2, NOVEMBER 2003, www.nature.com/naturematerials, the disclosure ofwhich is incorporated herein in its entirety.

In some embodiments Cu is selectively deposited by an ALD typedeposition process. In some embodiments Cu is selectively deposited by acyclical deposition process. In some embodiments Cu is selectivelydeposited on a first surface of a substrate relative to a second,different surface of the substrate by an ALD type process comprisingalternately and sequentially contacting the substrate with a first Cuprecursor and a second reactant.

In some embodiments a substrate comprising a first surface and a secondsurface is provided and a metal, here Cu, is selectively deposited on afirst surface of a substrate by an ALD type deposition processcomprising multiple cycles, each cycle comprising:

contacting the surface of a substrate with a vaporized first metalprecursor, for example Cu acetamidinate;

removing excess metal precursor and reaction by products, if any, fromthe surface;

contacting the surface of the substrate with a second vaporizedreactant, for example H₂;

removing from the surface excess second reactant and any gaseousby-products formed in the reaction between the metal precursor layer onthe first surface of the substrate and the second reactant, and;

repeating the contacting and removing steps until a metal, here Cu, thinfilm of the desired thickness has been formed.

As mentioned above, in some embodiments one or more surfaces of thesubstrate may be treated in order to enhance deposition on one surfacerelative to one or more different surfaces prior to beginning thedeposition process. In some embodiments the second, non-metal surfacecan be treated to provide an OH-terminated surface, or can bedeactivated, such as by passivation, prior to deposition of the metal,here Cu.

Although the illustrated Cu deposition cycle begins with contacting thesubstrate with the first Cu precursor, in other embodiments thedeposition cycle begins with contacting the substrate with the secondreactant. It will be understood by the skilled artisan that contactingthe substrate surface with the first Cu precursor and second reactantare interchangeable in the ALD cycle.

When the Cu precursor contacts the substrate, the Cu precursor may format least a monolayer, less than a monolayer, or more than a monolayer.

In some embodiments the Cu precursor comprises a Cu acetamidinate or aderivative thereof. In some embodiments the Cu precursor comprises Cu(I)N,N′-di-sec-butylacetamidinate [Cu(sec-Bu₂-AMD)]₂. The Cu precursor maybe provided with the aid of an inert carrier gas, such as argon.

In some embodiments the second reactant comprises hydrogen. In someembodiments the second reactant comprises hydrogen gas.

Selective Deposition of Metal or Metal Oxide on Dielectric

As mentioned above, in some embodiments a metal or metal oxide materialis selectively deposited on a first hydrophilic surface of a substraterelative to a second, different surface, such as a conductive surface,metal surface, or H-terminated surface of the same substrate.

In some embodiments metal or metal oxide deposition on the first surfaceof the substrate relative to the second surface of the substrate is atleast about 90% selective, at least about 95% selective, at least about96%, 97%, 98% or 99% or greater selective. In some embodiments metal ormetal oxide deposition only occurs on the first surface and does notoccur on the second surface. In some embodiments metal or metal oxidedeposition on the first surface of the substrate relative to the secondsurface of the substrate is at least about 80% selective, which may beselective enough for some particular applications. In some embodimentsdeposition on the first surface of the substrate relative to the secondsurface of the substrate is at least about 50% selective, which may beselective enough for some particular applications.

In some embodiments the second surface is treated, or deactivated, toinhibit deposition of a metal or metal oxide thereon. For example, ametal surface may be treated by oxidation to provide a metal oxidesurface. In some embodiments a Cu, Ru, W, Al, Ni, Co, or other noblemetal surface is oxidized to facilitate selective deposition on adielectric surface relative to the Cu, Ru, W, Al, Ni, Co, or other noblemetal surface. In some embodiments the second surface comprises a metalselected individually from Cu, Ni, Co, Al, W, Ru and other noble metals.In some embodiments the second surface is a Cu surface. In someembodiments the second surface is a Ni surface. In some embodiments thesecond surface is a Co surface. In some embodiments the second surfaceis an Al surface. In some embodiments the second surface is a W surface.In some embodiments the second surface is a Ru surface. In someembodiments the second surface comprises a noble metal.

In some embodiments the conductive surface comprises an oxide such asCuOx, NiOx, CoOx or RuOx or another noble metal oxide. In someembodiments a conductive surface may no longer be conductive after ithas been treated. For example, a conductive surface may be treated priorto or at the beginning of the selective deposition process, such as byoxidation, and the treated surface may no longer be conductive.

In some embodiments the second surface is not a hydrophilic surface. Insome embodiments a hydrophilic surface may be treated so that it is nolonger a hydrophilic surface. In some embodiments the second surface isa Si surface. In some embodiments the second surface is an H-terminatedsurface. In some embodiments the second surface is treated, for exampleby contacting with a chemical that provides a —SiH₃ terminated surface.In some embodiments a Si surface is treated prior to deposition of ametal or metal oxide on a first surface.

In some embodiments the second, metal, surface is oxidized prior todeposition of a metal or metal oxide on a first surface. In someembodiments the second, metal, surface is oxidized at the beginning ofthe deposition process, for example, during the first phase of adeposition cycle. In some embodiments the second, metal, surface isoxidized prior to the first phase of a deposition cycle.

In some embodiments the second surface may be passivated to inhibitdeposition thereon. In some embodiments, for example, the second surfacemay be passivated with alkylsilyl-groups. For example, in someembodiments a second surface is passivated such that it comprisesalkylsilyl-groups, in order to facilitate selective deposition on adielectric surface relative to the second surface. The passivation mayfacilitate selective deposition on the dielectric surface relative to atreated metal surface. For example, deposition of an oxide on the metalsurface may be inhibited by the passivation. In some embodimentspassivation does not include formation of a SAM or a similar monolayerhaving a long carbon chain on the metal surface.

In some embodiments the material selectively deposited on a firstsurface of a substrate relative to a second surface is a metal. In someembodiments the material selectively deposited on a first surface of asubstrate relative to a second surface is a metal oxide. In someembodiments the metal selectively deposited is Fe. In some embodimentsthe metal oxide selectively deposited is a Ni, Fe, or Co oxide. In someembodiments the metal selectively deposited is Ni. In some embodimentsthe metal selectively deposited is Co. In some embodiments selectivedeposition of a metal oxide may be achieved by oxidation of aselectively deposited metal. In some embodiments a metal is firstselectively deposited and subsequently oxidized to form a metal oxide.In some embodiments a metal is not oxidized after being selectivelydeposited. In some embodiments oxidation of a selectively depositedmetal to form a metal oxide may also result in OH surface terminationson the metal oxide. In some embodiments oxidation may result in OHsurface terminations on the substrate. In some embodiments oxidation mayresult in OH surface terminations on both the metal oxide surface andthe second surface of the substrate.

ALD type selective deposition processes, such as the process as shown inFIG. 2 and described above can be used to selectively deposit a metal ormetal oxide on a first surface of a substrate relative to a secondsurface. In some embodiments the first precursor is a first metalprecursor. In some embodiments the first precursor is a first metaloxide precursor. In some embodiments the second reactant comprises anoxygen source. In some embodiments the second reactant comprises anoxygen source as described herein in relation to selective deposition ofa dielectric on a dielectric.

In some embodiments a metal is selective deposited on a first surface ofa substrate relative to a second, different surface of the samesubstrate. In some embodiments a metal is selectively deposited bydecomposition of a metal precursor. In some embodiments a metal oxide isselectively deposited by adsorption of metal compounds, followed byoxidation of the metal compound to form a metal oxide. In someembodiments a metal oxide is selectively deposited by self-limitingadsorption of metal compounds, followed by oxidation of the metalcompound to form up to a molecular layer of metal oxide.

In some embodiments Ni is selectively deposited on a second surface ofthe substrate relative to a dielectric surface of the same substrate. Insome embodiments Ni is selectively deposited by decomposition ofbis(4-N-ethylamino-3-penten-2-N-ethyliminato)nickel (II). In someembodiments NiO is selectively deposited by adsorption of Ni compounds,such as bis(4-N-ethylamino-3-penten-2-N-ethyliminato)nickel (II)followed by oxidation of the Ni compound to form NiO. In someembodiments NiO is selectively deposited by self-limiting adsorption ofNi compounds, such asbis(4-N-ethylamino-3-penten-2-N-ethyliminato)nickel (II) followed byoxidation of the Ni compound to form up to molecular layer of NiO.

Suitable nickel precursors may be selected by the skilled artisan. Ingeneral, nickel compounds where the metal is bound or coordinated tooxygen, nitrogen, carbon or a combination thereof are preferred. In someembodiments the nickel precursors are organic compounds. In someembodiments the nickel precursor is a metalorganic compound. In someembodiments the nickel precursor is a metal organic compound comprisingbidentate ligands. In some embodiments the nickel precursor isbis(4-N-ethylamino-3-penten-2-N-ethyliminato)nickel (ii).

In some embodiments, nickel precursors can be selected from the groupconsisting of nickel betadiketonate compounds, nickel betadiketiminatocompounds, nickel aminoalkoxide compounds, nickel amidinate compounds,nickel cyclopentadienyl compounds, nickel carbonyl compounds andcombinations thereof. In some embodiments, X(acac)y or X(thd)y compoundsare used, where X is a metal, y is generally, but not necessarilybetween 2 and 3 and thd is 2,2,6,6-tetramethyl-3,5-heptanedionato. Someexamples of suitable betadiketiminato (e.g., Ni(pda)2) compounds arementioned in U.S. Patent Publication No. 2009-0197411 Al, the disclosureof which is incorporated herein in its entirety. Some examples ofsuitable amidinate compounds (e.g., Ni(iPr-AMD)2) are mentioned in U.S.Patent Publication No. 2006-0141155 A1, the disclosure of which isincorporated herein in its entirety.

The nickel precursor may also comprise one or more halide ligands. Inpreferred embodiments, the precursor is a nickel betadiketiminatocompound, such bis(4-N-ethylamino-3-penten-2-N-ethyliminato)nickel (II)[Ni(EtN-EtN-pent)2], nickel ketoiminate, suchbis(3Z)-4-nbutylamino-pent-3-en-2-one-nickel(II), nickel amidinatecompound, such as methylcyclopentadienyl-isopropylacetamidinate-nickel(II), nickel betadiketonato compound, such as Ni(acac)2, Ni(thd)2 ornickel cyclopentadienyl compounds, such Ni(Cp)2, Ni(MeCp)2, Ni(EtCp)2 orderivatives thereof, such asmethylcyclopentadienyl-isopropylacetamidinate-nickel (II). In morepreferred embodiment, the precursor isbis(4-N-ethylamino-3-penten-2-N-ethyliminato)nickel (II).

In some embodiments the first Ni precursor isbis(4-N-ethylamino-3-penten-2-N-ethyliminato)nickel (II).

In some embodiments the first precursor used in a selective depositionprocess for depositing Co or Co oxide on a first surface of a substraterelative to a second surface is a Co precursor. In some embodiments theCo precursor is a Co beta-diketoiminato compound. In some embodimentsthe Co precursor is a Co ketoiminate compound. In some embodiments theCo precursor is a Co amidinate compound. In some embodiments the Coprecursor is a Co beta-diketonate compound. In some embodiments the Coprecursor contains at least one ketoimine ligand or a derivativethereof. In some embodiments the Co precursor contains at least oneamidine ligand or a derivative thereof. In some embodiments the Coprecursor contains at least one ketonate ligand or a derivative thereof

In some embodiments the first precursor used in a selective depositionprocess for depositing Fe or Fe oxide on a first surface of a substraterelative to a second surface is a Fe precursor. In some embodiments theFe precursor is Cp₂Fe or derivative thereof. In some embodiments the Feprecursor contains at least one cyclopentadienyl ligand (Cp),substituted cyclopentadienyl ligand or a derivative thereof. In someembodiments the Fe precursor contains at least one carbonyl ligand (—CO)or a derivative thereof. In some embodiments the Fe precursor containsat least one carbonyl ligand (—CO) and at least one organic ligand, suchas a cyclopentadienyl ligand (Cp) or a substituted cyclopentadienylligand or a derivative thereof. In some embodiments the Fe precursor isFe(acac)₂. In some embodiments the Fe precursor is Fe-alkoxide, such asiron(III) tert-butoxide (Fe₂(O^(t)Bu)₆). In some embodiments the Feprecursor is Fe(CO)₅.

In some embodiments the second reactant in an ALD process forselectively depositing a metal or metal oxide is selected from hydrogenand forming gas. In other embodiments the second reactant may be analcohol, such as EtOH.

In some embodiments the second reactant is an organic reducing agent.The organic reducing agents preferably have at least one functionalgroup selected from the group consisting of alcohol (—OH), as mentionedabove, or aldehyde (—CHO), or carboxylic acid (—COOH).

Reducing agents containing at least one alcohol group may be selectedfrom the group consisting of primary alcohols, secondary alcohols,tertiary alcohols, polyhydroxy alcohols, cyclic alcohols, aromaticalcohols, halogenated alcohols, and other derivatives of alcohols.

Preferred primary alcohols have an —OH group attached to a carbon atomwhich is bonded to another carbon atom, in particular primary alcoholsaccording to the general formula (I):

[R1-OH  (I)

[wherein R1 is a linear or branched C1-C20 alkyl or alkenyl groups,preferably methyl, ethyl, propyl, butyl, pentyl or hexyl. Examples ofpreferred primary alcohols include methanol, ethanol, propanol, butanol,2-methyl propanol and 2-methyl butanol.

Preferred secondary alcohols have an —OH group attached to a carbon atomthat is bonded to two other carbon atoms. In particular, preferredsecondary alcohols have the general formula (II):

wherein each R1 is selected independently from the group of linear orbranched C1-C20 alkyl and alkenyl groups, preferably methyl, ethyl,propyl, butyl, pentyl or hexyl. Examples of preferred secondary alcoholsinclude 2-propanol and 2-butanol.

Preferred tertiary alcohols have an —OH group attached to a carbon atomthat is bonded to three other carbon atoms. In particular, preferredtertiary alcohols have the general formula (III):

wherein each R1 is selected independently from the group of linear orbranched C1-C20 alkyl and alkenyl groups, preferably methyl, ethyl,propyl, butyl, pentyl or hexyl. An example of a preferred tertiaryalcohol is tert-butanol.

Preferred polyhydroxy alcohols, such as diols and triols, have primary,secondary and/or tertiary alcohol groups as described above. Examples ofpreferred polyhydroxy alcohol are ethylene glycol and glycerol.

Preferred cyclic alcohols have an —OH group attached to at least onecarbon atom which is part of a ring of 1 to 10, more preferably 5-6carbon atoms.

Preferred aromatic alcohols have at least one —OH group attached eitherto a benzene ring or to a carbon atom in a side chain. Examples ofpreferred aromatic alcohols include benzyl alcohol, o-, p- and m-cresoland resorcinol.

Preferred halogenated alcohols have the general formula (IV):

CHnX3-n-R2-OH  (IV)

wherein X is selected from the group consisting of F, Cl, Br and I, n isan integer from 0 to 2 and R2 is selected from the group of linear orbranched C1-C20 alkyl and alkenyl groups, preferably methyl, ethyl,propyl, butyl, pentyl or hexyl. More preferably X is selected from thegroup consisting of F and Cl and R2 is selected from the groupconsisting of methyl and ethyl. An example of a preferred halogenatedalcohol is 2,2,2-trifluoroethanol.

Other derivatives of alcohols that may be used include amines, such asmethyl ethanolamine.

Preferred reducing agents containing at least one aldehyde group (—CHO)are selected from the group consisting of compounds having the generalformula (V), alkanedial compounds having the general formula (VI),halogenated aldehydes and other derivatives of aldehydes.

Thus, in some embodiments reducing agents are aldehydes having thegeneral formula (V):

R3-CHO  (V)

wherein R3 is selected from the group consisting of hydrogen and linearor branched C1-C20 alkyl and alkenyl groups, preferably methyl, ethyl,propyl, butyl, pentyl or hexyl. More preferably, R3 is selected from thegroup consisting of methyl or ethyl. Examples of preferred compoundsaccording to formula (V) are formaldehyde, acetaldehyde andbutyraldehyde.

In other embodiments reducing agents are aldehydes having the generalformula (VI):

OHC—R4-CHO  (VI)

wherein R4 is a linear or branched C1-C20 saturated or unsaturatedhydrocarbon. Alternatively, the aldehyde groups may be directly bondedto each other (R4 is null).

Reducing agents containing at least one —COOH group may be selected fromthe group consisting of compounds of the general formula (VII),polycarboxylic acids, halogenated carboxylic acids and other derivativesof carboxylic acids.

Thus, in some embodiment preferred reducing agents are carboxylic acidshaving the general formula (VII):

R5-COOH  (VII)

wherein R5 is hydrogen or linear or branched C1-C20 alkyl or alkenylgroup, preferably methyl, ethyl, propyl, butyl, pentyl or hexyl, morepreferably methyl or ethyl. Examples of preferred compounds according toformula (VII) are formic acid and acetic acid, most preferably formicacid (HCOOH).

Selective Deposition of Dielectric on Dielectric

As mentioned above, in some embodiments a dielectric material isselectively deposited on a first dielectric surface of a substraterelative to a second, different surface, such as a conductive surface,metal surface, or H-terminated surface of the same substrate.

In some embodiments dielectric deposition on the first surface of thesubstrate relative to the second surface of the substrate is at leastabout 90% selective, at least about 95% selective, at least about 96%,97%, 98% or 99% or greater selective. In some embodiments dielectricdeposition only occurs on the first surface and does not occur on thesecond surface. In some embodiments dielectric deposition on the firstsurface of the substrate relative to the second surface of the substrateis at least about 80% selective, which may be selective enough for someparticular applications. In some embodiments deposition on the firstsurface of the substrate relative to the second surface of the substrateis at least about 50% selective, which may be selective enough for someparticular applications.

In some embodiments the second surface is treated, or deactivated, toinhibit deposition of a dielectric thereon. For example, a metal surfacemay be treated by oxidation to provide a metal oxide surface. In someembodiments a Cu, Ru, Al, Ni, Co, or other noble metal surface isoxidized to facilitate selective deposition on a dielectric surfacerelative to the Cu, Ru, Al, Ni, Co, or other noble metal surface. Insome embodiments the second surface comprises a metal selectedindividually from Cu, Ni, Co, Al, W, Ru and other noble metals. In someembodiments the second surface is a Cu surface. In some embodiments thesecond surface is a Ni surface. In some embodiments the second surfaceis a Co surface. In some embodiments the second surface is an Alsurface. In some embodiments the second surface is a Ru surface. In someembodiments the second surface comprises a noble metal.

In some embodiments the conductive surface comprises an oxide such asCuOx, NiOx, CoOx or RuOx or another noble metal oxide. In someembodiments a conductive surface may no longer be conductive after ithas been treated. For example, a conductive surface may be treated priorto or at the beginning of the selective deposition process, such as byoxidation, and the treated surface may no longer be conductive.

In some embodiments the second, metal, surface is oxidized prior todeposition of a dielectric on a first surface. In some embodiments thesecond, metal, surface is oxidized at the beginning of the depositionprocess, for example, during the first phase of a deposition cycle. Insome embodiments the second, metal surface is oxidized prior to thefirst phase of a deposition cycle. In some embodiments the second,metal, surface is purposefully oxidized with an oxygen source. In someembodiments the second, metal, surface is oxidized in the ambient airand/or contains native oxide. In some embodiments the second, metal,surface contains an oxide which has been deposited.

In some embodiments the second surface may be passivated to inhibitdeposition thereon. In some embodiments, for example, the second surfacemay be passivated with alkylsilyl-groups. For example, in someembodiments a second surface is passivated such that it comprisesalkylsilyl-groups, in order to facilitate selective deposition on adielectric surface relative to the second surface. The passivation mayfacilitate selective deposition on the dielectric surface relative tothe treated metal surface. For example, deposition of an oxide on thefirst metal surface may be inhibited by the passivation. In someembodiments passivation does not include formation of a SAM or a similarmonolayer having a long carbon chain on the metal surface.

As mentioned above, in some embodiments a dielectric material isselectively deposited on a first dielectric surface of a substraterelative to a second, different surface, such as a metal surface of thesame substrate. In some embodiments the second, metal surface istreated, or deactivated, to inhibit deposition of a dielectric thereon.For example, a metal surface may be treated by oxidation to provide ametal oxide surface. In some embodiments a Cu, Ru or other noble metalsurface is oxidized to facilitate selective deposition on a dielectricsurface relative to the Cu or Ru surface. In some embodiments the metalsurface may be passivated, for example with alkylsilyl-groups. Forexample, in some embodiments a Sb surface is passivated such that itcomprises alkylsilyl-groups, in order to facilitate selective depositionon a dielectric surface relative to the Sb surface.

Selective Deposition of GeO₂ on Dielectric

GeO₂ may be deposited by an ALD type process on a first dielectricsurface of a substrate relative to a second, different surface of thesame substrate. In some embodiments the second surface may be aconductive surface, a metal surface, or an H-terminated surface. In someembodiments the GeO₂ is deposited by a method as described in U.S.application Ser. No. 13/802,393, filed Mar. 13, 2013, which is herebyincorporated by reference. In some embodiments the dielectric surface isa hydrophilic OH-terminated surface. However, in some embodiments thedielectric surface may comprise Si-H groups. For example, the dielectricsurface can be a SiO₂ surface, a low-k surface comprising OH-groups, aSi-H surface, or a GeO₂ surface. The second surface may be, for example,a Cu, Ru, Al, Ni, Co, or other noble metal surface. In some embodimentsthe second surface comprises a metal selected individually from Cu, Ni,Co, Al, W, Ru and other noble metals. In some embodiments the secondsurface is a Cu surface. In some embodiments the second surface is a Nisurface. In some embodiments the second surface is a Co surface. In someembodiments the second surface is an Al surface. In some embodiments thesecond surface is a Ru surface. In some embodiments the second surfacecomprises a noble metal. As discussed above, in some embodiments adielectric surface may be treated to increase the amount of OH-groups onthe surface. In some embodiments the second surface may be an oxide. Insome embodiments the second surface may be a metal surface that has beenoxidized.

In some embodiments the conductive surface comprises an oxide such asCuOx, NiOx, CoOx or RuOx or another noble metal oxide. In someembodiments a conductive surface may no longer be conductive after ithas been treated. For example, a conductive surface may be treated priorto or at the beginning of the selective deposition process, such as byoxidation, and the treated surface may no longer be conductive.

In some embodiments the second, metal, surface is purposefully oxidizedwith an oxygen source. In some embodiments the second, metal, surfacehas oxidized in the ambient air and/or contains native oxide. In someembodiments the second, metal, surface contains an oxide which has beendeposited.

As previously discussed, in some embodiments, the metal surface isoxidized prior to deposition in order to facilitate selective depositionof GeO₂ on the dielectric surface relative to the metal surface. In someembodiments a second reactant in a selective deposition process mayserve to oxidize the metal surface. Thus, in some embodiments the secondreactant is provided first in the initial ALD cycle, or prior to thefirst ALD cycle. In some embodiments the metal surface is oxidized priorto beginning the selective deposition process.

In some embodiments the metal surface is passivated prior to depositionin order to facilitate selective deposition of GeO₂ on the dielectricsurface relative to the other surface, such as a surface comprisingmetal. For example, a metal surface can be provided with alkylsilylgroups. In some embodiments the other surface can be passivated,preferably with an alkylamine passivation compound prior to selectivedeposition of GeO₂ on a dielectric surface. In some other embodimentsthe other surface can be passivated, preferably with an alkylaminepassivation precursor during the deposition on GeO₂ on a dielectricsurface. In some embodiments an alkylamine passivation precursor may bepulsed into a reaction chamber in between pulses of Ge-precursor and asecond reactant, or prior to or after each cycle, or prior to or afterevery n^(th) cycle, where n is a number that may depend on the processconditions, reactors, substrate surfaces, and properties of the desiredselectively deposited film. The needed frequency of passivation maydepend on the process conditions, reactors, substrate surfaces, andproperties of the selectively deposited film. In some embodimentssurface passivation can be performed during each GeO₂ selectivedeposition cycle, for example an alkylamine precursor may contact thesubstrate during a GeO₂ selective deposition cycle, or HCOOH may contactthe substrate during a GeO₂ selective deposition cycle, or both aprecursor comprising an alkylamine and HCOOH may contact the substrateduring a GeO₂ deposition cycle. In some embodiments more than onepassivation precursor may be used. Exemplary alkylamine passivationprecursors for use in passivation can be of the formula:

H—(NR^(I)R^(II))

Wherein R^(I) can be independently selected from the group consisting ofhydrogen, alkyl and substituted alkyl, preferably C1-C4 alkyl; and

R^(II) can be independently selected from the group consisting of alkyland substituted alkyl, preferably C1-C4 alkyl.

Specific exemplary alkylamine passivation precursors include H—N(Me₂),H—N(EtMe) and H—N(Et)₂

In some embodiments GeO₂ deposition on the first surface of thesubstrate relative to the second surface of the substrate is at leastabout 90% selective, at least about 95% selective, at least about 96%,97%, 98% or 99% or greater selective. In some embodiments GeO₂deposition only occurs on the first surface and does not occur on thesecond surface. In some embodiments GeO₂ deposition on the first surfaceof the substrate relative to the second surface of the substrate is atleast about 80% selective, which may be selective enough for someparticular applications. In some embodiments deposition on the firstsurface of the substrate relative to the second surface of the substrateis at least about 50% selective, which may be selective enough for someparticular applications.

In some embodiments a substrate comprising a first surface and a secondsurface is provided and a dielectric, here GeO₂, is selectivelydeposited on a first surface of a substrate by an ALD-type processcomprising multiple cycles, each cycle comprising:

contacting the surface of a substrate with a vaporized first precursor,for example a Ge-alkylamide;

removing excess first precursor and reaction by products, if any, fromthe surface;

contacting the surface of the substrate with a second vaporizedreactant, for example H₂O;

removing from the surface excess second reactant and any gaseousby-products formed in the reaction between the first precursor layer onthe first surface of the substrate and the second reactant, and;

repeating the contacting and removing steps until a dielectric, hereGeO₂, thin film of the desired thickness has been formed on a firstsurface of the substrate.

As mentioned above, in some embodiments one or more surfaces of thesubstrate may be treated in order to enhance deposition on one surfacerelative to one or more different surfaces prior to beginning thedeposition process. In some embodiments the second, metal surface isdeactivated, such as by passivation or oxidation prior to the depositionof the dielectric, here GeO₂.

In some embodiments germanium oxide, preferably GeO₂, is deposited fromalternately and sequentially contacting the substrate with a Geprecursor and a second reactant, such as water, ozone, oxygen plasma,oxygen radicals, or oxygen atoms. In some embodiments the secondreactant is not water. The Ge precursor preferably comprises Ge(OEt)4 orTDMAGe.

The Ge precursor employed in the ALD type processes may be solid,liquid, or gaseous material under standard conditions (room temperatureand atmospheric pressure), provided that the Ge precursor is in vaporphase before it is contacted with the substrate surface. Contacting thesurface of a substrate with a vaporized precursor means that theprecursor vapor is in contact with the surface of the substrate for alimited period of time. Typically, the contacting time is from about0.05 seconds to about 10 seconds. However, depending on the substratetype and its surface area, the contacting time may be even higher thanabout 10 seconds.

In some embodiments, the reactants and reaction by-products can beremoved from the substrate surface by stopping the flow of secondreactant while continuing the flow of an inert carrier gas. In someembodiments the substrate is moved such that different reactantsalternately and sequentially contact the surface of the substrate in adesired sequence for a desired time. In some embodiments the removingsteps are not performed. In some embodiments no reactant may be removedfrom the various parts of a chamber. In some embodiments the substrateis moved from a part of the chamber containing a first precursor toanother part of the chamber containing the second reactant. In someembodiments the substrate is moved from a first reaction chamber to asecond, different reaction chamber.

Preferably, for a 300 mm wafer in a single wafer ALD reactor, thesubstrate surface is contacted with a Ge precursor for from about 0.05seconds to about 10 seconds, more preferably for from about 0.1 secondsto about 5 seconds and most preferably for from about 0.3 seconds toabout 3.0 seconds. The substrate surface is contacted with the secondprecursor preferably for from about 0.05 seconds to about 10 seconds,more preferably for from about 0.1 seconds to about 5 seconds, mostpreferably for from about 0.2 seconds to about 3.0 seconds. However,contacting times can be on the order of minutes in some cases. Theoptimum contacting time can be readily determined by the skilled artisanbased on the particular circumstances.

As mentioned above, in some embodiments the Ge precursor is Ge(OEt)₄ orTDMAGe. In some embodiments, where the Ge precursor is an ethoxideprecursor, the first surface may comprise Si-H groups. Other possiblegermanium precursors that can be used in some embodiments are describedbelow. In some embodiments, the Ge precursor is Ge(OMe)₄. In someembodiments the Ge-precursor is not a halide. In some embodiments theGe-precursor may comprise a halogen in at least one ligand, but not inall ligands.

In certain preferred embodiments GeO₂ is selectively deposited on afirst surface of a substrate relative to a second, different surface ofthe substrate by an ALD type process, comprising multiple cycles, eachcycle comprising alternately and sequentially contacting the substratewith vapor phase Ge— alkylamide and a second reactant comprising water.

In certain preferred embodiments GeO₂ is selectively deposited on afirst surface of a substrate relative to a second, different surface ofthe substrate by an ALD type process, comprising multiple cycles, eachcycle comprising alternately and sequentially contacting the substratewith a vapor phase Ge precursor with the formula Ge(NR^(I)R^(II))₄, anda second reactant comprising water, wherein R^(I) can be independentlyselected from the group consisting of hydrogen, alkyl and substitutedalkyl, wherein R^(I) can be preferably independently selected from thegroup consisting of C1-C3 alkyls, such as methyl, ethyl, n-propyl, andi-propyl, most preferably methyl or ethyl; and wherein R^(II) can beindependently selected from the group consisting of alkyl andsubstituted alkyl, wherein R^(II) can be preferably independentlyselected from the group consisting of C1-C3 alkyls, such as methyl,ethyl, n-propyl, and i-propyl, most preferably methyl or ethyl.

The second reactant may be an oxygen-containing gas pulse and can be amixture of oxygen and inactive gas, such as nitrogen or argon. In someembodiments the second reactant may be a molecular oxygen-containinggas. The preferred oxygen content of the second reactant gas is fromabout 10% to about 25%. Thus, in some embodiments the second reactantmay be air. In some embodiments, the second reactant is molecularoxygen. In some embodiments, the second reactant comprises an activatedor excited oxygen species. In some embodiments, the second reactantcomprises ozone. The second reactant may be pure ozone or a mixture ofozone, molecular oxygen, and another gas, for example an inactive gassuch as nitrogen or argon. Ozone can be produced by an ozone generatorand it is most preferably introduced into the reaction space with theaid of an inert gas of some kind, such as nitrogen, or with the aid ofoxygen. In some embodiments, ozone is provided at a concentration fromabout 5 vol-% to about 40 vol-%, and preferably from about 15 vol-% toabout 25 vol-%. In other embodiments, the second reactant is oxygenplasma.

In some embodiments, the surface of the substrate is contacted withozone or a mixture of ozone and another gas. In other embodiments, ozoneis formed inside a reactor, for example by conducting oxygen containinggas through an arc. In other embodiments, an oxygen containing plasma isformed in a reactor. In some embodiments, a plasma may be formed in situon top of the substrate or in close proximity to the substrate. In otherembodiments, a plasma is formed upstream of a reaction chamber in aremote plasma generator and plasma products are directed to the reactionchamber to contact the substrate. As will be appreciated by the skilledartisan, in the case of a remote plasma, the pathway to the substratecan be optimized to maximize electrically neutral species and minimizeion survival before reaching the substrate.

In some embodiments the second reactant is a second reactant other thanwater. Thus, in some embodiments water is not provided in any ALD cyclefor selectively depositing GeO₂.

A number of different Ge precursors can be used in the selectivedeposition processes. In some embodiments the Ge precursor istetravalent (i.e. Ge has an oxidation state of +IV). In someembodiments, the Ge precursor is not divalent (i.e., Ge has an oxidationstate of +II). In some embodiments, the Ge precursor may comprise atleast one alkoxide ligand. In some embodiments, the Ge precursor maycomprise at least one amine or alkylamine ligand. In some embodimentsthe Ge precursor is a metal-organic or organometallic compound. In someembodiments the Ge precursor comprises at least one halide ligand. Insome embodiments the Ge precursor does not comprise a halide ligand.

For example, Ge precursors from formulas (1) through (9), as previouslydiscussed above, may be used in some embodiments.

In some embodiments the Ge precursor comprises at least one amine oralkylamine ligand, such as those presented in formulas (2) through (6)and (8) and (9), and the oxygen precursor comprises water.

In some embodiments the Ge precursor comprises at least one alkoxy,amine or alkylamine ligand. In some embodiments the GeO₂ is deposited byan ALD process using water and a Ge-alkylamine precursor. In someembodiments the Ge precursor is Ge(NMe₂)₄ or Ge(NEt₂)₄ or Ge(NEtMe)₄.

Before starting the deposition of the film, the substrate is typicallyheated to a suitable growth temperature, as discussed above. Thepreferred deposition temperature may vary depending on a number offactors such as, and without limitation, the reactant precursors, thepressure, flow rate, the arrangement of the reactor, and the compositionof the substrate including the nature of the material to be depositedon.

The processing time depends on the thickness of the layer to be producedand the growth rate of the film. In ALD, the growth rate of a thin filmis determined as thickness increase per one cycle. One cycle consists ofthe contacting and removing steps of the precursors and the duration ofone cycle is typically between about 0.2 seconds and about 30 seconds,more preferably between about 1 second and about 10 seconds, but it canbe on order of minutes or more in some cases, for example, where largesurface areas and volumes are present.

In some embodiments the GeO₂ film formed is a pure GeO₂ film.Preferably, aside from minor impurities no other metal or semi-metalelements are present in the film. In some embodiments the film comprisesless than 1-at % of metal or semi-metal other than Ge. In someembodiments the GeO₂ film is stoichiometric. In some embodiments, a pureGeO₂ film comprises less than about 5-at % of any impurity other thanhydrogen, preferably less than about 3-at % of any impurity other thanhydrogen, and more preferably less than about 1-at % of any impurityother than hydrogen.

In some embodiments, the GeO₂ film formed has step coverage of more thanabout 80%, more preferably more than about 90%, and most preferably morethan about 95% in structures which have high aspect ratios. In someembodiments high aspect ratio structures have an aspect ratio that ismore than about 3:1 when comparing the depth or height to the width ofthe feature. In some embodiments the structures have an aspect ratio ofmore than about 5:1, or even an aspect ratio of 10:1 or greater.

Selective Deposition of SiO₂ on Dielectric

SiO₂ may be deposited by an atomic layer deposition type process on afirst dielectric surface of a substrate relative to a second surface ofthe same substrate. In some embodiments the dielectric surface is ahydrophilic OH-terminated surface. For example, the dielectric surfacecan be a SiO₂ surface, a low-k surface, preferably comprising OH-groups,or GeO₂ surface. In some embodiments the second surface may be aconductive surface, a metal surface, or a H-terminated surface. Thesecond surface may be, for example, a Cu, Ru, Al, Ni, Co, or other noblemetal surface. In some embodiments the second surface comprises a metalselected individually from Cu, Ni, Co, Al, W, Ru and other noble metals.In some embodiments the second surface is a Cu surface. In someembodiments the second surface is a Ni surface. In some embodiments thesecond surface is a Co surface. In some embodiments the second surfaceis an Al surface. In some embodiments the second surface is a Rusurface. In some embodiments the second surface comprises a noble metal.As discussed above, in some embodiments a dielectric surface may betreated to increase the amount of OH-groups on the surface.

In some embodiments the conductive surface comprises an oxide such asCuOx, NiOx, CoOx or RuOx or another noble metal oxide. In someembodiments a conductive surface may no longer be conductive after ithas been treated. For example, a conductive surface may be treated priorto or at the beginning of the selective deposition process, such as byoxidation, and the treated surface may no longer be conductive.

In some embodiments the second, metal, surface is purposefully oxidizedwith an oxygen source. In some embodiments the second, metal, surfacehas oxidized in the ambient air and/or contains native oxide. In someembodiments the second, metal, surface contains an oxide which has beendeposited.

In some embodiments SiO₂ deposition on the first surface of thesubstrate relative to the second surface of the substrate is at leastabout 90% selective, at least about 95% selective, at least about 96%,97%, 98% or 99% or greater selective. In some embodiments SiO₂deposition only occurs on the first surface and does not occur on thesecond surface. In some embodiments SiO₂ deposition on the first surfaceof the substrate relative to the second surface of the substrate is atleast about 80% selective, which may be selective enough for someparticular applications. In some embodiments deposition on the firstsurface of the substrate relative to the second surface of the substrateis at least about 50% selective, which may be selective enough for someparticular applications.

In a preferred embodiment SiO₂ is selectively deposited by an ALD typeprocess using an aminosilane as the Si precursor and ozone as the secondreactant. In some embodiments the SiO₂ is deposited by an ALD processusing ozone and an aminosilane, such as bis(diethylamino)silaneprecursor. Such methods are known in the art and can be adapted todeposit selectively on the dielectric material relative to a metal.

In some embodiments, the metal surface is oxidized prior to depositionin order to facilitate selective deposition of SiO₂ on the dielectricsurface relative to the metal surface. In some embodiments an oxygensource in a selective deposition process may serve to oxidize the metalsurface. Thus, in some embodiments the second reactant is provided firstin the initial ALD cycle, or prior to the first ALD cycle. In someembodiments the metal surface is oxidized prior to beginning theselective deposition process.

In some embodiments the metal surface is passivated prior to depositionin order to facilitate selective deposition of SiO₂ on the dielectricsurface relative to the metal surface. For example, the metal surfacecan be provided with alkylsilyl groups.

In some embodiments a substrate comprising a first surface and a secondsurface is provided and a dielectric, here SiO₂, is selectivelydeposited on a first surface of a substrate by an ALD-type processcomprising multiple cycles, each cycle comprising:

contacting the surface of a substrate with a vaporized first precursor,for example an aminosilane;

removing excess first precursor and reaction by products, if any, fromthe surface;

contacting the surface of the substrate with a second vaporizedreactant, for example ozone;

removing from the surface excess second reactant and any gaseousby-products formed in the reaction between the first precursor layer onthe first surface of the substrate and the second reactant, and;

repeating and removing steps until a dielectric, here SiO₂, thin film ofthe desired thickness has been formed on a first surface of thesubstrate.

As mentioned above, in some embodiments one or more surfaces of thesubstrate may be treated in order to enhance deposition on one surfacerelative to one or more different surfaces prior to beginning thedeposition process. In some embodiments the second, metal surface isdeactivated, such as by passivation or In some embodiments thedeposition process is operated at a temperature lower than 450° C. Insome embodiments the deposition process if operated at 400° C. In someembodiments the entire deposition process is carried out at the sametemperature.

In some embodiments the SiO₂ selective deposition can be carried out ata wide range of pressure conditions, but it is preferred to operate theprocess at reduced pressure. The pressure in a reaction chamber istypically from about 0.01 to about 500 mbar or more. However, in somecases the pressure will be higher or lower than this range, as can bereadily determined by the skilled artisan. The pressure in a singlewafer reactor is preferably maintained between about 0.01 mbar and 50mbar, more preferably between about 0.1 mbar and 10 mbar. The pressurein a batch ALD reactor is preferably maintained between about 1 mTorrand 500 mTorr, more preferably between about 30 mTorr and 200 mTorr.

In some embodiments the SiO₂ deposition temperature is kept low enoughto prevent thermal decomposition of the gaseous source chemicals. On theother hand, the deposition temperature is kept high enough to provideactivation energy for the surface reactions, to prevent thephysisorption of source materials and minimize condensation of gaseousreactants in the reaction space. Depending on the reactants andreactors, the deposition temperature is typically about 20° C. to about500° C., preferably about 150° C. to about 350° C., more preferablyabout 250° C. to about 300° C.

The silicon source temperature is preferably set below the deposition orsubstrate temperature. This is based on the fact that if the partialpressure of the source chemical vapor exceeds the condensation limit atthe substrate temperature, controlled layer-by-layer growth of the thinfilm is compromised. In some embodiments, the silicon source temperatureis from about 30 to about 150° C. In some embodiments the silicon sourcetemperature is greater than about 60° C. during the deposition. In someembodiments, where greater doses are needed, for example in batch ALD,the silicon source temperature is from about 90° C. to about 200° C.,preferably from about 130° C. to about 170° C.

In some embodiments, the reactants and reaction by-products can beremoved from the substrate surface by stopping the flow of secondreactant while continuing the flow of an inert carrier gas. In someembodiments the substrate is moved such that different reactantsalternately and sequentially contact the surface of the substrate in adesired sequence for a desired time. In some embodiments the removingsteps are not performed. In some embodiments no reactant may be removedfrom the various parts of a chamber. In some embodiments the substrateis moved from a part of the chamber containing a first precursor toanother part of the chamber containing the second reactant. In someembodiments the substrate is moved from a first reaction chamber to asecond, different reaction chamber.

In some embodiments SiO₂ is selectively deposited using an ALD typeprocess as described herein.

In some embodiments the growth rate of the thin film comprising silicondioxide is preferably above 0.7 Å/cycle. In other embodiments the growthrate is above 0.8 Å/cycle and in still other embodiments the growth rateis above 1.0 Å/cycle, and preferably in the range of 1.0 to 1.2 Å/cycle.

In some embodiments the selectively deposited silicon dioxide has lessthan 2 at-% of nitrogen as an impurity. In other embodiments the SiO₂comprise less than 1 at-% of nitrogen, or even less than 0.5 at-%nitrogen as an impurity. Similarly, in some embodiments the SiO₂comprise less than 1 at-% carbon as an impurity and in some cases lessthan 0.5 at-% carbon as an impurity.

In some embodiments the selectively deposited silicon oxide has a stepcoverage of more than 80%, in other embodiments preferably more than 90%and in other embodiments preferably more than 95%.

In certain preferred embodiments SiO₂ is selectively deposited on afirst surface of a substrate relative to a second, different surface ofthe substrate by an ALD type process, comprising multiple cycles, eachcycle comprising alternately and sequentially contacting the substratewith vapor phase BDEAS and a second reactant comprising ozone.

For the simplicity, SiO₂, silicon oxide, silica, and silicon dioxide areinterchangeable as used herein and generally refer to the same compound.

Si Precursors

In some embodiments the silicon precursor can comprise silane, siloxane,or silazane compounds. In some embodiments the SiO₂ is deposited usingprecursors as described in U.S. Pat. No. 7,771,533, which is herebyincorporated by reference. For example, the Si precursor from theformulas (1) through (3) below may be used in some embodiments.

Si_(m)L_(2m+2)  (1)

Si_(y)O_(y-1)L_(2y+2)  (2)

Si_(y)NH_(y-1)L_(2y+2)  (3)

Wherein L can be independently selected from the group consisting of F,Cl, Br, I, alkyl, aryl, alkoxy, vinyl, cyano, amino, silyl, alkylsilyl,alkoxysilyl, silylene an alkylsiloxane. In some embodiments alkyl andalkoxy groups can be linear or branched and contain at least onesubstituent. In some embodiments alkyl and alkoxy groups contain 1-10carbon atoms, preferably 1-6 carbon atoms.

In some embodiments the silicon precursor can preferably compriseamino-substituted silanes and silazanes, such as 3-aminoalkyltrialkoxysilanes, for example 3-aminopropyltriethoxy silaneNH₂—CH₂CH₂CH₂—Si(O—CH₂CH₃)₃(AMTES) and 3-aminopropyltrimethoxy silane(NH₂—CH₂CH₂CH₂—Si(O—CH₃)₃(AMTMS) and hexa-alkyldisilazane(CH₃)₃Si—NH—Si(CH₃)₃ (HDMS).

In some embodiments the SiO₂ is deposited using precursors as describedin U.S. Pat. No. 8,501,637 which is hereby incorporated by reference. Insome embodiments, the silicon precursor is preferably a disilane and hasa Si—Si bond. Organic compounds having a Si—Si bond and an NH_(x) groupeither attached directly to silicon (to one or more silicon atoms) or toa carbon chain attached to silicon are used in some embodiments. In someembodiments organosilicon compounds are used, which may or may notcomprise Si—Si bonds. More preferably the silicon compound has theformula:

R^(III) _(3-x)(R^(II)R^(I)N)_(x)—Si—Si—(N—R^(I)R^(II))_(y)R^(III)_(3-y),  (I)

wherein,

x is selected from 1 to 3;

y is selected from 1 to 3;

R^(I) is selected from the group consisting of hydrogen, alkyl, andsubstituted alkyl;

R^(II) is selected from the group consisting of alkyl and substitutedalkyl; and

R^(III) is selected from the group consisting of hydrogen, hydroxide(—OH), amino (—NH₂), alkoxy, alkyl, and substituted alkyl;

and wherein the each x, y, R^(III), R^(II) and R^(I) can be selectedindependently from each other.

In some embodiments the silicon compound ishexakis(monoalkylamino)disilane:

(R^(II)—NH)₃—Si—Si—(NH—R^(II))₃  (II)

In other embodiments the silicon compound ishexakis(ethylamino)disilane:

(Et-NH)₃—Si—Si—(NH-Et)₃  (II)

In other embodiments the silicon compound is (CH₃—O)₃—Si—Si—(O—CH₃)₃(IV)

In some embodiments, the silicon compound ishexakis(monoalkylamino)disilane (R^(II)—NH)₃—Si—Si—(NH—R″)₃ and R^(II)is selected from the group consisting of alkyl and substituted alkyl.

In some embodiments the SiO₂ is deposited using precursors as describedin U.S. Publication No. 2009/0232985 which is hereby incorporated byreference. In some embodiments the deposition temperature can be as lowas room temperature and up to 500° C., with an operating pressure of0.1-100 Torr (13 to 13300 Pa). High quality films, with very low carbonand hydrogen contents, are preferably deposited between 200 and 400° C.at a pressure between 0.1-10 Torr (13 to 1330 Pa).

In some embodiments the Si precursor can be selected from the groupconsisting of:

Bis(diethylamino)silane SiH₂(NEt₂)₂

BDMAS Bis(dimethylamino)silane SiH₂(NMe₂)₂

TriDMAS Tris(diethylamino)silane SiH(NMe₂)₃

Bis(trimethylsilylamino)silane SiH₂(NHSiMe₃)₂

TEAS Tetrakis(ethylamino)silane Si(NHEt)₄

[TEOS Tetrakis(ethoxy)silane Si(OEt)₄

BTESE Bis(triethoxysilyl)ethane (EtO)₃Si—CH₂—CH₂—Si(OEt)₃

In some embodiments the Si precursor is an aminosilane of the generalformula (R1R2N)nSiH_(4-x), where x is comprised between 1 and 4, whereR1 and R2 are independently H or a C1-C6 linear, branched or cycliccarbon chains. Preferably the Si precursor is an aminosilane of thegeneral formula (R1R2N)nSiH₂, where R1 and R2 are preferablyindependently selected from C1-C4 linear, branched or cyclic carbonchains. In some embodiments the alkylaminosilane isbis(diethylamino)silane (BDEAS), bis(dimethylamino)silane (BDMAS) ortris(dimethylamino)silane (TriDMAS).

In some embodiments the Si precursor is a silane (silane, disilane,trisilane, trisilylamine) of the general formula (SiH₃)xR where may varyfrom 1 to 4 and wherein R is selected from the comprising H, N, O, CH₂,CH₂—CH₂, SiH₂, SiH, Si with the possible use of a catalyst in ALDregime. Preferably the silane is a C-free silane. Most preferably, thesilane is trisilylamine. In some embodiments a very small amount (<1%)of catalyst may introduced into the reactor. The silanes described abovecan be difficult to use in ALD conditions, as their adsorption on asilicon wafer is not favorable. In some embodiments the use of acatalyst helps the adsorption of silane on the first surface of thesubstrate or the underlying layer. In some embodiments, the introductionof the catalyst is simultaneous with the silane. In some embodiments thecatalyst is an amine or a metal-containing molecule, preferably amolecule containing an early transition metal, most preferably ahafnium-containing molecule, such as Hf(NEt₂)4. In some embodiments, thecatalyst is C-free.

In some embodiments the SiO₂ is deposited using precursors as describedin U.S. Publication No. 2007/0275166 which is hereby incorporated byreference.

In some embodiments the Si precursor used in the selective depositionprocess is an organoaminosilane precursor and it is represented byformula A as follows:

In this class of compounds R and R¹ are selected from the groupconsisting of C₂-C₁₀ alkyl groups, linear, branched, or cyclic,saturated or unsaturated, aromatic, alkylamino groups, heterocyclic,hydrogen, silyl groups, with or without substituents, and R and R¹ alsobeing combinable into a cyclic group. Representative substituents arealkyl groups and particularly the C₁₋₄ alkyl groups, such as ethyl,propyl and butyl, including their isomeric forms, cyclic groups such ascyclopropyl, cyclopentyl, and cyclohexyl. Illustrative of some of thepreferred compounds within this class are represented by the formulas:

where n is 1-6, preferably 4 or 5.

In some embodiments the silicon precursor is an organoaminosilane whichhas two silyl groups pendant from a single nitrogen atom as representedby formula B.

As with the R groups of the Class A compounds, R is selected from thegroup consisting of C₂-C₁₀ alkyl groups, linear, branched, or cyclic,saturated or unsaturated, aromatic, alkylamino groups, and heterocyclic.Specific R groups include methyl, ethyl, propyl, allyl, butyl,dimethylamine group, and cyclic groups such as cyclopropyl, cyclopentyl,and cyclohexyl. Illustrative compounds are represented by the formulas:

It has been found though that even though the above organoaminosilanesare suitable for producing silicon oxide films on a first surface of asubstrate, organoaminosilanes of formula A are preferred.

In some embodiments the silicon precursor can be formed during the ALDtype deposition process. In some embodiments a new vapor phase siliconprecursor is formed which is then also able to adsorb onto a firstsurface of the substrate. This can be referred to as in situ formationof silicon precursors In some embodiments in situ formed siliconprecursors can be a silane compound, for example with the formulaSiL₁L₂L₃L₄, wherein L₁ represents an amino group, such as an alkyl aminogroup and L₂-L₄ represent alkyl or alkoxy group. This silane compound isformed, for example when the first surface of a substrate is contactedwith hexa-alkyldisilazane at 350-450° C. at a pressure of 0.1-50 mbar.

Second Reactants

In some embodiments a second reactant as previously disclosed for use ina GeO₂ selective deposition process can be used with the above mentionedSi precursors. In some embodiments the second reactant is ozone. In someembodiments the second reactant is molecular oxygen. In some embodimentsthe second reactant is one or more of the following compounds:

oxides of nitrogen, such as N₂O, NO and NO₂;

oxyhalide compounds, for example chlorodioxide (ClO₂) and perchloroacid(HClO₄);

peracids, for example perbenzoic acid and peracetic acid;

alcohols, such as methanol and ethanol;

various radicals, for example oxygen radicals (O) or hydroxyl radical(OH); and

hydrogen peroxide (H₂O₂).

In some embodiments the oxygen precursor is not plasma. In someembodiments the oxygen precursor comprises oxygen radicals. As discussedabove, in some embodiments the selective deposition processes disclosedherein do not utilize plasma, such as direct plasma as the direct plasmacan harm the second surface of the substrate. In some instances,however, a selective deposition process could utilize radicals made byplasma as a reactant which are not too energetic, for example oxygenradicals made by plasma that do not destroy or degrade a surface of thesubstrate.

According to some embodiments, at least one compound or the at least oneoxygen containing gas is on the first surface of the substrate prior tocontacting the surface with another compound and/or at least one oxygencontaining gas.

In some embodiments, contacting the substrate surface with each compoundand/or oxygen containing gas is followed by the removal of the compoundand/or oxygen containing gas from the surface of the substrate, forexample by injection of a purge gas, such as an inert gas, into areaction chamber, while in some embodiments contacting the surface ofthe substrate with compounds and/or gas is repeated until the desiredSiO₂ film thickness is obtained. The pressure inside a reaction chambershall be preferably below 100 Torr, more preferably below 2 Torr.Preferably, the H content in the selectively deposited SiO₂ film is lessthan 8.1021 atoms/cc.

In some embodiments, an ozone containing gas is a gas mixture comprisingoxygen and ozone with a ratio O₃/O₂ below 30% vol., preferably between5% and 20% vol. Preferably, the oxygen/ozone gas mixture is diluted intoan inert gas, preferably nitrogen.

Selective Deposition of TiO₂ on Dielectric

In some embodiments TiO₂ may be deposited by an ALD type process on afirst dielectric surface of a substrate relative to a second, differentsurface of the same substrate. In some embodiments the second surfacemay be a conductive surface, a metal surface, or an H-terminatedsurface. In some embodiments TiO₂ is deposited by a method as describedin Viljami Pore, dissertation “Atomic Layer Deposition andPhotocatalytic Properties of Titanium Dioxide Thin Films”, 2010, page29, available athttps://helda.helsinki.fi/bitstream/handle/10138/21126/atomicla.pdf?sequence=1,which is hereby incorporated by reference. In some embodiments thedielectric surface is a hydrophilic OH-terminated surface. For example,the dielectric surface can be a SiO₂ surface, a low-k surface,preferably comprising OH-groups, or a GeO₂ surface. The second surfacemay be, for example, a Cu, Ru, Al, Ni, Co, or other noble metal surface.In some embodiments the second surface comprises a metal selectedindividually from Cu, Ni, Co, Al, W, Ru and other noble metals. In someembodiments the second surface is a Cu surface. In some embodiments thesecond surface is a Ni surface. In some embodiments the second surfaceis a Co surface. In some embodiments the second surface is an Alsurface. In some embodiments the second surface is a Ru surface. In someembodiments the second surface comprises a noble metal.

As discussed above, in some embodiments a dielectric surface may betreated to increase the amount of OH-groups on the surface. In someembodiments the second surface may be an oxide. In some embodiments thesecond surface may be a metal surface that has been oxidized.

In some embodiments the conductive surface comprises an oxide such asCuOx, NiOx, CoOx or RuOx or another noble metal oxide. In someembodiments a conductive surface may no longer be conductive after ithas been treated. For example, a conductive surface may be treated priorto or at the beginning of the selective deposition process, such as byoxidation, and the treated surface may no longer be conductive.

In some embodiments the second, metal, surface is purposefully oxidizedwith an oxygen source. In some embodiments the second, metal, surfacehas oxidized in the ambient air and/or contains native oxide. In someembodiments the second, metal, surface contains an oxide which has beendeposited.

As previously discussed, in some embodiments, the metal surface isoxidized prior to deposition in order to facilitate selective depositionof TiO₂ on the dielectric surface relative to the metal surface. In someembodiments a second reactant in a selective deposition process mayserve to oxidize the metal surface. Thus, in some embodiments the secondreactant is provided first in the initial ALD cycle, or prior to thefirst ALD cycle. In some embodiments the metal surface is oxidized priorto beginning the selective deposition process.

In some embodiments the metal surface is passivated prior to depositionin order to facilitate selective deposition of TiO₂ on the dielectricsurface relative to the metal surface. For example, the metal surfacecan be provided with alkylsilyl groups.

In some embodiments TiO₂ deposition on the first surface of thesubstrate relative to the second surface of the substrate is at leastabout 90% selective, at least about 95% selective, at least about 96%,97%, 98% or 99% or greater selective. In some embodiments TiO₂deposition only occurs on the first surface and does not occur on thesecond surface. In some embodiments TiO₂ deposition on the first surfaceof the substrate relative to the second surface of the substrate is atleast about 80% selective, which may be selective enough for someparticular applications. In some embodiments deposition on the firstsurface of the substrate relative to the second surface of the substrateis

In some embodiments TiO₂ is deposited by an ALD type process using, forexample, Ti(OMe)₄ as a titanium reactant and water as a second reactant.In some embodiments TiO₂ is deposited by an ALD type process using, forexample, TiF₄ as a titanium reactant and water as a second reactant. Insome embodiments TiO₂ is deposited by an ALD type process using, forexample, TiCl₄ as a titanium reactant and water as a second reactant.Methods for depositing TiO₂ by ALD are known in the art and can beadapted to selectively deposit TiO₂ on a dielectric surface relative toa second, different surface.

In some embodiments TiO₂ is selectively deposited by an ALD type processon a first surface of a substrate. In some embodiments a substratecomprising a first surface and a second, different surface is providedand a dielectric, here TiO2, is selectively deposited on a first surfaceof a substrate by an ALD-type process comprising multiple cycles, eachcycle comprising:

contacting the surface of a substrate with a vaporized first precursor,for example a Ti alkylamine precursor;

removing excess first precursor and reaction by products, if any, fromthe surface;

contacting the surface of the substrate with a second vaporizedreactant, for example H₂O, or ozone;

removing from the surface excess second reactant and any gaseousby-products formed in the reaction between the first precursor layer onthe first surface of the substrate and the second reactant, and;

repeating the contacting and removing steps until a dielectric, hereTiO2, thin film of the desired thickness has been formed on a firstsurface of the substrate.

As mentioned above, in some embodiments one or more surfaces of thesubstrate may be treated in order to enhance deposition on one surfacerelative to one or more different surfaces prior to beginning thedeposition process.

Suitable titanium reactant may be selected by the skilled artisan. Insome embodiments the titanium precursor may comprise a titanium halide.In some embodiments the titanium precursor may be at least one of TiCl₄,TiI₄, and TiF₄. In some embodiments the titanium precursor may comprisea titanium alkoxide. In some embodiments the titanium precursor may beat least one of Ti(OME)₄, Ti(OEt)₄, and Ti(O^(i)Pr)₄. In someembodiments that titanium precursor may comprise a titanium alkylamide.In some embodiments the titanium precursor may comprise a titaniumalkylamine compound. In some embodiments the titanium precursor may beat least one of Ti(NMe₂)₄, Ti(NEt₂)₄, and Ti(NMeEt)₄. In someembodiments that titanium precursor may comprise a heterolepticprecursor. In some embodiments the titanium precursor may be at leastone of Ti(O^(i)Pr)₂(dmae)₂, Ti(Me₅Cp)(OMe)₃, Ti(MeCp)(OMe)₃,TiCp(NMe₂)₃, TiMe₅Cp(NMe₂)₃, and Ti(O^(i)Pr)₂(thd)₂. In some embodimentsthe titanium precursor may comprises a titanium alkylamine.

In some embodiments the second reactant may comprise an oxygencontaining reactant. In some embodiments the second reactant cancomprise oxygen or a mixture of oxygen and another gas. In someembodiments the second reactant may comprises diatomic oxygen, or amixture of diatomic oxygen and another gas. In some embodiments thesecond reactant may comprise ozone. In some embodiments the secondreactant may comprise a mixture of ozone and another gas, for example acarrier gas. In some embodiments the second reactant may comprise anoxygen containing compound, such as H₂O₂, H₂O and/or an organicperoxide. In some embodiments the second precursor comprises water. Insome embodiments the second precursor comprises water plasma.

In some embodiments a second reactant may form oxygen inside a reactionchamber, for example by decomposing oxygen containing compounds. In someembodiments a second reactant may comprise catalytically formed oxygen.In some embodiments the catalytical formation of a second reactantcomprising oxygen may include conducting a vaporized aqueous solution ofH₂O₂ over a catalytic surface, for example platinum or palladium. Insome embodiments a catalytic surface may be located inside a reactionchamber. In some embodiments a catalytic surface may not be locatedinside the reaction chamber.

In some embodiments the second reactant comprises free-oxygen or ozone,or molecular oxygen. In some embodiments the second reactant is puremolecular diatomic oxygen, but can also be a mixture of oxygen andinactive gas, for example, nitrogen or argon. In some embodiments, thesurface of the substrate is contacted with ozone or a mixture of ozoneand another gas. In other embodiments, ozone is formed inside a reactor,for example by conducting oxygen containing gas through an arc. In otherembodiments, an oxygen containing plasma is formed in a reactor. In someembodiments, a plasma may be formed in situ on top of the substrate orin close proximity to the substrate. In other embodiments, a plasma isformed upstream of a reaction chamber in a remote plasma generator andplasma products are directed to the reaction chamber to contact thesubstrate. As will be appreciated by the skilled artisan, in the case ofa remote plasma, the pathway to the substrate can be optimized tomaximize electrically neutral species and minimize ion survival beforereaching the substrate.

In some embodiments the second precursor is not plasma. In someembodiments the second precursor comprises oxygen radicals. As discussedabove, in some embodiments the selective deposition processes disclosedherein do not utilize plasma, such as direct plasma as the direct plasmacan harm the second surface of the substrate. In some instances,however, a selective deposition process could utilize radicals made byplasma as a reactant which are not too energetic, for example oxygenradicals made by plasma that do not destroy or degrade a surface of thesubstrate.

Methods for depositing TiO₂ by ALD type processes are known in the artand can be adapted to selectively deposit TiO₂.

In some embodiments the Ti alkoxide is decomposed from Ti alkoxideprecursor on an OH terminated surface to form TiO₂ directly.

As noted above, processes described herein enable use of ALD typedeposition techniques to selectively deposit TiO₂. The ALD typedeposition process is mostly surface-controlled (based on controlledreactions at the first substrate surface) and thus has the advantage ofproviding high conformality at relatively low temperatures. However, insome embodiments, the titanium precursor may at least partiallydecompose. Accordingly, in some embodiments the ALD type processdescribed herein is a pure ALD process in which no decomposition ofprecursors is observed. In other embodiments reaction conditions, suchas reaction temperature, are selected such that a pure ALD process isachieved and no precursor decomposition takes place.

In some embodiments TiO₂ is selectively deposited by a vapor depositionprocess on a first surface of a substrate. In some embodiments asubstrate comprising a first surface comprising surface —OH groups and asecond, different surface is provided. As discussed above, in someembodiments one or more surfaces of the substrate may be treated inorder to enhance selective deposition on one surface relative to one ormore different surface prior to beginning the deposition process, forexample by increasing the amount of —OH groups on the first dielectricsurface. In some embodiments TiO₂ is selectively deposited on a firstsurface of a substrate by a vapor deposition process comprising:

contacting the surface of the substrate comprising OH, NH_(x), or SH_(x)terminations with a vaporized first precursor, for example a titaniumalkoxide, and;

decomposing titanium alkoxide on the surface to form TiO₂.

Dual Selective Growth of Ru Metal and Dielectric

Referring to FIGS. 3A and 3B, and in some embodiments dual selectivedeposition of a Ru film and a dielectric film 300, 301 can beaccomplished on a substrate comprising a first metal surface 340, 341and a second dielectric surface 330, 331. In some embodiments Ru can beselectively deposited on the first metal surface 340, 341 by a selectivedeposition process 310, 311 as described herein above. In someembodiments the Ru precursor used in the dual selective depositionprocess is a Cp-based ruthenium precursor, such as Ru(EtCp)₂, while thesecond reactant comprises at least one of O₂ and O₃.

In some embodiments Ru is selectively deposited on a first metal surface340, 341 of a substrate. In some embodiments the first metal surface340, 341 comprises a CuO surface. In some embodiments the CuO surface isreduced to a Cu surface prior to selective deposition of Ru by exposureto a reducing agent according to methods described herein above. In someembodiments the first surface 340, 341 may comprise a W surface.

In some embodiments the first surface 340, 341 may comprise a CuOsurface, which is reduced to a Cu surface, and a thin W layer isselectively deposited on the Cu surface prior to beginning the selectivedeposition of Ru. In some embodiments the first surface 340,341 maycomprise a Cu surface on which a thin W layer is selectively depositedprior to beginning selective deposition of Ru. In some embodiments athin W layer is selectively deposited on a first surface 340, 341according to method described herein above prior to beginning selectivedeposition of Ru 310, 311. In some embodiments a thin W layer isselectively deposited on a first metal surface 340, 341 by a selectivedeposition process described herein above, wherein disilane is the firstprecursor and WF₆ is the W precursor. In some embodiments a second,dielectric surface 330, 331 of the substrate is deactivated prior toselectively depositing a thin W layer on the first surface of thesubstrate. In some embodiments the second surface 330, 331 isdeactivated by removing OH groups from the second surface. In someembodiments the second surface 330, 331 is deactivated by exposing thesubstrate to a silylation compound, for example Me₃SiNMe₂.

In some embodiments the second surface 330, 331 of the substrate maycomprise a dielectric surface as described herein above. In someembodiments the second surface 330, 331 of the substrate may comprise,for example a SiO₂, MgO, GeO₂, or Al₂O₃ surface. In some embodiments thesecond surface 330, 331 of the substrate may comprise OH, NH_(x), orSH_(x) terminations.

In some embodiments, the selective deposition of Ru 310, 311 continuesuntil a desired thickness of Ru is obtained on the first surface. Insome embodiments selective deposition of the Ru 310, 311 continues untila desired number of deposition cycles is completed. For example, in someembodiments up to about 1-50 deposition cycles for selectivelydepositing Ru are carried out.

In some embodiments, after Ru has been selectively deposited on a firstsurface 340, 341 of a substrate relative to a second, dielectric surface330, 331 of the same substrate, the Ru surface may optionally bepassivated against deposition of a dielectric by any of the methodsdescribed herein above. Additionally, in some embodiments anypassivation treatment that was optionally provided on the second surface330, 331 may optionally be removed. In some embodiments the secondsurface 330, 331 may optionally be activated according to methodsdescribed herein above.

After any optional surface treatment has been provided, a dielectric isselectively deposited 320, 321 on the second surface 330, 331 of thesubstrate relative to the selectively deposited Ru surface of the samesubstrate according to methods described herein above. Referring to FIG.3A, and in some embodiments the selectively deposited dielectric maycomprise GeO₂. Referring to FIG. 3B, and in some embodiments theselectively deposited dielectric may comprise SiO₂. In some embodimentsGeO₂ is selectively deposited 320 on a second surface 330 of thesubstrate using a selective deposition process as described abovewherein the Ge precursor comprises Ge(NMe₂)₄ and the second reactantcomprises H₂O. In some embodiments SiO₂ is selectively deposited 321 ona second surface 331 of the substrate using a selective depositionprocess as described above wherein the Si precursor comprisesH₂Si(NEt₂)₂ and the second reactant comprises O₃.

In some embodiments, the selective deposition of the dielectric 320, 321continues until a desired thickness of dielectric material is obtainedon the second surface. In some embodiments selective deposition of thedielectric material 320, 321 continues until a desired number ofdeposition cycles is completed. For example, in some embodiments up toabout 1-50 deposition cycles for selectively depositing the dielectricmaterial are carried out.

In some embodiments deposition on the first surface 340, 341 of thesubstrate relative to the second surface 330, 331 of the substrate,and/or on the second surface of the substrate 330, 331 relative to thefirst surface of the substrate 340, 341 is at least about 90% selective,at least about 95% selective, at least about 96%, 97%, 98% or 99% orgreater selective. In some embodiments deposition only occurs on thefirst surface and does not occur on the second surface or only occurs onthe second surface and does not occur on the first surface.

In some embodiments deposition on the first surface of the substrate340, 341 relative to the second surface of the substrate 330, 331 and/oron the second surface of the substrate relative to the first surface isat least about 80% selective, which may be selective enough for someparticular applications. In some embodiments the deposition on the firstsurface of the substrate relative to the second surface of the substrateis at least about 50% selective, which may be selective enough for someparticular application.

In some embodiments after a dielectric has been selectively deposited320, 321 on a second surface of a substrate 330, 331 relative to aselectively deposited Ru surface of the same substrate any passivationlayer or surface treatment that may be present on the selectivelydeposited Ru surface may optionally be removed according to any of themethods described herein above. In some embodiments passivation of thefirst surface can be performed during each dielectric deposition cycle,as described herein above. For example, an alkylamine passivationcompound or HCOOH, or both may contact the substrate during a dielectricdeposition cycle, for example GeO₂, to passivate the first surface.

Although the dual selective deposition processes 300, 301 illustratedabove proceeded with selective deposition of Ru before the selectivedeposition of a dielectric, one of skill in the art will understand thata dual selective deposition process may begin with the selectivedeposition of either Ru or a dielectric prior to the selectivedeposition of a second material.

Example 1

Conditions for lack of Ru deposition have been observed, in particularfor processes using Ru(EtCp)₂ as an Ru precursor and O₂/O₃ as a secondreactant on SiO₂ and other dielectric surfaces like MgO, GeO₂, Al₂O₃. Inaddition Ru deposition tends not to occur when attempting ALD withRu(EtCp)₂ as a Ru precursor and O₂/O₃ as a second reaction without along incubation period, that is many ALD cycles can occur without anygrowth on the dielectric surface. In general, it has been observed thatRu(EtCp)₂ does not react with Si—OH groups. Additionally, other Ruprecursors disclosed herein may bring Ru to the dielectric surfaceduring a first cycle, but will then have a long growth incubation timebefore any Ru film growth starts. Without being bound by any oneparticular theory, it is thought that Ru thin film growth requires Ruparticles that are large enough to dissociate O₂, which will not occurat the dielectric surface.

As Ru is selectively deposited on a first surface of the substraterelative to a second dielectric surface of the same substrate, adielectric material is preferably selectively deposited on a second,dielectric surface of the substrate relative to the deposited Ru surfaceof the same substrate. Two different Ru surface terminations have beentested for selectivity with regards to dielectric deposition, namely aCp (cyclopentadienyl) ligand termination and an oxygen termination. Foralkyl amide type metal precursors as disclosed herein above, an oxygenterminated selectively deposited Ru surface was observed to be the mostde-active against selective dielectric deposition as disclosed hereinabove. Tables 1 and 2 show the LEIS analysis results below; after 5cycles of GeO₂ deposition the fraction of Ge on the surface is stillvery low.

TABLE 1 Surface fraction of Ru and Ge after GeO₂ ALD on a EtCpterminated Ru surface. Number of GeO₂ Ru Surface Ge as fraction ALDCycles Fraction of surface area 0 97.2 0 1 90.1 3.5 2 104.9 4.9 5 103.715.8 10 82.4 26.2 20 45.1 46.6 250 0 100

TABLE 2 Surface fraction of Ru and Ge after GeO₂ ALD on a O₂ terminatedRu surface. Number of GeO₂ Ru Surface Ge as fraction ALD Cycles Fractionof surface area 0 94 0 1 94.2 0.1 2 100.3 1.5 5 105.8 4 10 85.8 9.1 2075.6 16.2 50 35.6 45.6 250 0 100

Without being bound by any one particular theory, it is possible that Cpsurface terminations leave uncoordinated Ru sites for alkyl amide typeprecursors to interact with, which is some embodiments can be passivatedby an alkylamine pulse prior to selective deposition of an oxide. Insome embodiments uncoordinated Ru sites may be passivated by contactingthe substrate with a passivating agent during every dielectric selectivedeposition cycle, for example a compound comprising an alkylamine cancontact the substrate during every GeO₂ or SiO₂ selective depositioncycle.

Again, without being bound by any one theory, it is possible that theoxygen used in an Ru selective deposition process may oxidize a Cusurface. Furthermore, In some embodiments Ru selective depositiontemperature may be relatively high and the two metals can intermix,stopping the Ru film growth. Therefore, in a modified process flow itmay be preferably for a thin W layer to be selectively deposited fromWF₆ and disilane prior to starting Ru selective deposition. However, toachieve selective deposition of W on the Cu surface relative to thedielectric surface, the dielectric surface is preferably deactivated byremoving the OH groups with a silylation compound, such as Me₃SiNMe₂.

Dual Selective Growth of Cu or CuO and Dielectric

Referring to FIG. 4, and in some embodiments dual selective depositionof Cu and a dielectric 400 can be accomplished on a substrate comprisinga first metal surface 440 and a second, different surface 430. In someembodiments Cu can be selectively deposited 420 on the first metalsurface 440 by a selective deposition process as described herein above.In some embodiments the Cu precursor used in the dual selectivedeposition 420 process is Cu amidinate.

In some embodiments the first metal surface 440 comprises a CuO surface.In some embodiments the CuO surface is reduced to a Cu surface prior toselective deposition of Cu 420 by exposure to a reducing agent 450according to methods described herein above. In some embodiments thesecond surface 430 of the substrate may comprise a dielectric surface asdescribed herein above. In some embodiments the second surface 430 ofthe substrate may comprise, for example a SiO₂, MgO, GeO₂, or Al₂O₃surface. In some embodiments the second surface 430 of the substrate maycomprise OH, NH_(x), or SH_(L) terminations. In some embodiments eitherthe first or second surface may optionally be treated to enhanceselective deposition according to the methods described herein aboveprior to beginning selective deposition.

In some embodiments a dielectric is selectively deposited 410 on thesecond surface 430 of the substrate relative to the first surface 440 ofthe same substrate according to methods described herein above. In someembodiments the selectively deposited dielectric may comprise GeO₂, asis depicted in FIG. 4. In some embodiments the selectively depositeddielectric may comprise SiO₂. In some embodiments GeO₂ is selectivelydeposited 410 on a second surface 430 of the substrate using a selectivedeposition process as described above wherein the Ge precursor comprisesGe(NMe₂)₄ and the second reactant comprises H₂O.

In some embodiments, the selective deposition of the dielectric 410continues until a desired thickness of dielectric material is obtainedon the second surface 430. In some embodiments selective deposition ofthe dielectric material 410 continues until a desired number ofdeposition cycles is completed. For example, in some embodiments up toabout 1-50 deposition cycles for selectively depositing the dielectricmaterial are carried out.

In some embodiments after selective deposition of a dielectric 410 on asecond surface of the substrate the substrate may optionally be treated450 to enhance selective deposition according to the methods describedherein above. In some embodiments this may comprise exposing the firstsurface 440 to a reducing agent. In some embodiments a CuO surface maybe exposed to HCOOH to thereby be reduced to a Cu surface.

In some embodiments Cu is selectively deposited 420 on a first surface440 of the substrate relative to the selectively deposited dielectricsurface of the same substrate. In some embodiments Cu is selectivelydeposited by decomposition of Cu amidinate as described herein above.

In some embodiments, the selective deposition of Cu 420 continues untila desired thickness of Cu is obtained on the first surface. In someembodiments deposition on the first surface 440 of the substraterelative to the second surface 430 of the substrate, and/or on thesecond surface 430 of the substrate relative to the first surface 440 ofthe substrate is at least about 90% selective, at least about 95%selective, at least about 96%, 97%, 98% or 99% or greater selective. Insome embodiments deposition only occurs on the first surface 440 anddoes not occur on the second surface 430 or only occurs on the secondsurface and does not occur on the first surface.

In some embodiments deposition on the first surface 440 of the substraterelative to the second surface 430 of the substrate and/or on the secondsurface 430 of the substrate relative to the first surface 440 is atleast about 80% selective, which may be selective enough for someparticular applications. In some embodiments the deposition on the firstsurface of the substrate relative to the second surface of the substrateis at least about 50% selective, which may be selective enough for someparticular application.

In some embodiments after Cu has been selectively deposited 420 on afirst surface 440 of a substrate relative to a selectively depositeddielectric surface of the same substrate any passivation layer orsurface treatment that may be present on the selectively depositeddielectric surface may optionally be removed according to any of themethods described herein above. Additionally, in some embodiments theselectively deposited Cu film may be oxidized to form a CuO surfaceaccording to methods described herein above.

Although dual selective deposition process 400 illustrated above beganwith selective deposition of a dielectric 410 before the selectivedeposition of Cu 420, one of skill in the art will understand that adual selective deposition process may begin with the selectivedeposition of either Cu or a dielectric prior to the selectivedeposition of a second material.

Example 2

Conditions for lack of GeO₂ deposition have been observed, in particularfor deposition processes using Ge alkylamide and H₂O on a CuO surface ascompared to a W surface. As illustrated by Tables 3 and 4 below, after10 cycles of GeO₂ deposition the fraction of Ge on the CuO surface isessentially negligible (Table 3), whereas GeO₂ deposition hasdefinitively occurred after 10 cycles on a W surface (Table 4).

TABLE 3 Surface fraction of Cu and Ge after GeO₂ ALD on Cu(O). Number ofGeO₂ Cu (At. % Ge (At. % ALD Cycles fraction) fraction) 5 35 0 10 30 050 12 12 250 2 24

TABLE 4 Surface fraction of W and Ge after GeO₂ ALD on W. Number of GeO₂W (At. % Ge (At. % ALD Cycles fraction) fraction) 5 15 6 10 12 12 50 424 250 0 26

Further analysis was performed via LEIS, which showed essentially noGeO₂ film growth after 20 GeO₂ ALD cycles.

As for the selectivity of Cu precursors, Cu(I) amidinates have shownnon-reactivity towards SiO₂ surfaces, particularly Si—OH terminatedsurfaces. Without being bound by a particular theory, it is believedthat the similarities between GeO₂ and SiO₂ leads to similar surfacebehavior with respect to Cu(I) amidinates.

Dual Selective Growth of Sb and W

Referring to FIG. 5, and in some embodiments dual selective depositionof W and Sb 500 can be accomplished on a substrate comprising a firstsurface 540 and a second different surface 530. In some embodiments Sbcan be selectively deposited on a second surface 530 by a selectivedeposition process 510 as described herein above. In some embodimentsthe Sb precursors used in the selective deposition process 510 areSb(Si(CH₃)₃)₃ and SbCl₃. In some embodiments W can be selectivelydeposited on a first surface 540 by a selective deposition process 520as described herein above. In some embodiments the first precursor usedin the selective deposition process is disilane and the W precursor isWF₆.

In some embodiments dual selective deposition of W and Sb 500 can beaccomplished on a substrate comprising a first metal surface 540 and asecond, dielectric surface 530. In some embodiments W and Sb can beselectively deposited on a substrate comprising a first dielectricsurface and a second, different surface. In some embodiments the firstsurface 540 may comprise Cu, or CuO. In some embodiments the firstsurface may comprise a silicon surface. In some embodiments the firstsilicon surface can comprise Si—H terminations. In some embodiments thesecond surface 530 an comprise a hydrophilic surface. In someembodiments the second surface 530 can comprise an OH, NH_(x), or SH_(x)terminated surface. In some embodiments the second surface 530 cancomprise a SiO₂ or other dielectric surface.

In some embodiments the substrate is optionally treated 550 to enhanceselective deposition according to the methods described herein aboveprior to beginning selective deposition. In some embodiments the second,CuO surface is exposed to a reducing agent and reduced to a Cu surfaceat 550 according to methods described herein above prior to thebeginning of a selective deposition process. In some embodiments apreviously reduced metal surface may additionally be deactivatedaccording to the methods described herein above. In some embodiments thepreviously reduced surface may be deactivated by exposure to disilane toproduce a Si—H terminated surface.

In some embodiments Sb is selectively deposited 510 on the secondsurface 530 of the substrate relative to the first surface 540 of thesame substrate according to methods described herein above. In someembodiments the Sb precursors used in the selective deposition processare Sb(Si(CH₃)₃)₃ and SbCl₃.

In some embodiments, the selective deposition of Sb 510 continues untila desired thickness of Sb is obtained on the second surface 530. In someembodiments selective deposition of Sb 510 continues until a desirednumber of deposition cycles is completed. For example, in someembodiments up to about 1-50 deposition cycles for selectivelydepositing Sb are carried out.

In some embodiments after selective deposition of Sb 510 on a secondsurface 530 of the substrate may optionally be treated to enhanceselective deposition according to the methods described herein above.

In some embodiments W is selectively deposited 520 on a first surface540 of the substrate relative to the selectively deposited Sb surface ofthe same substrate. In some embodiments W is selectively deposited 520according to methods described herein above. In some embodiments thefirst precursor used in the selective deposition 520 process is disilaneand the W precursor is WF₆.

In some embodiments, the selective deposition of W 520 continues until adesired thickness of W is obtained on the first surface. In someembodiments deposition on the first surface 540 of the substraterelative to the second surface 530 of the substrate, and/or on thesecond surface 530 of the substrate relative to the first surface 540 ofthe substrate is at least about 90% selective, at least about 95%selective, at least about 96%, 97%, 98% or 99% or greater selective. Insome embodiments deposition only occurs on the first surface and doesnot occur on the second surface or only occurs on the second surface anddoes not occur on the first surface.

In some embodiments deposition on the first surface 540 of the substraterelative to the second surface 530 of the substrate and/or on the secondsurface of the substrate relative to the first surface is at least about80% selective, which may be selective enough for some particularapplications. In some embodiments the deposition on the first surface ofthe substrate relative to the second surface of the substrate is atleast about 50% selective, which may be selective enough for someparticular application.

In some embodiments after W has been selectively deposited 520 on afirst surface 540 of a substrate relative to a selectively deposited Sbsurface of the same substrate any passivation layer or surface treatmentthat may be present on the selectively deposited Sb surface mayoptionally be removed according to any of the methods described hereinabove.

Although dual selective deposition process 500 illustrated above beganwith selective deposition of Sb 510 before the selective deposition of W520, one of skill in the art will understand that a dual selectivedeposition process may begin with the selective deposition of either Wor Sb prior to the selective deposition of a second material.

Dual Selective Growth of Ni(O) and GeO₂

Referring to FIG. 6, and in some embodiments dual selective deposition600 of GeO₂ and Ni or NiO can be accomplished on a substrate comprisinga first surface 640 and a second, different surface 630. In someembodiments GeO₂ can be selectively deposited on a first surface 640 bya selective deposition process 620 as described herein above. In someembodiments Ni or NiO can be selectively deposited on the second surface630 by a selective deposition process 610 as described herein above. Insome embodiments the Ni precursor used in the selective depositionprocess 610 comprises a nickel betadiketiminato compound, suchbis(4-N-ethylamino-3-penten-2-N-ethyliminato)nickel (II)[Ni(EtN-EtN-pent)2]. In some embodiments the Ge precursor used in aselective deposition process 620 comprises Ge(NMe₂)₄ and the secondreactant comprises H₂O. In some embodiments Ni or NiO is preferablyselectively deposited prior to the selective deposition of GeO₂.

In some embodiments the first surface 640 comprises a dielectricmaterial. In some embodiments the first surface 640 comprises Si—Hsurface terminations. In some embodiments the first surface comprises ametal. In some embodiments the second surface 630 comprises ahydrophilic surface. In some embodiments the hydrophilic surfacecomprises a dielectric surface, such as SiO₂. In some embodiments thehydrophilic surface comprises OH, NH_(x), or SH_(x) terminations. Insome embodiments the substrate surface may optionally be treated toenhance selective deposition according to the methods described hereinabove.

In some embodiments Ni or NiO is selectively deposited 610 on a secondsurface 630 of the substrate relative to the selectively depositeddielectric surface of the same substrate. In some embodiments Ni or NiOis selectively deposited 610 by decomposition ofbis(4-N-ethylamino-3-penten-2-N-ethyliminato)nickel (II) as describedherein above. In some embodiments NiO is selectively deposited byadsorption of Ni compounds, such asbis(4-N-ethylamino-3-penten-2-N-ethyliminato)nickel (II) followed byoxidation of the Ni compound to form NiO. In some embodiments NiO isselectively deposited by self-limiting adsorption of Ni compounds, suchas bis(4-N-ethylamino-3-penten-2-N-ethyliminato)nickel (II) as describedherein above followed by oxidation of the Ni compound to form up tomolecular layer of NiO.

In some embodiments, the selective deposition of Ni or NiO 610 continuesuntil a desired thickness of Ni or NiO is obtained on the second surface630.

In some embodiments deposition on the first surface 640 of the substraterelative to the second surface 630 of the substrate, and/or on thesecond surface 630 of the substrate relative to the first surface 640 ofthe substrate is at least about 90% selective, at least about 95%selective, at least about 96%, 97%, 98% or 99% or greater selective. Insome embodiments deposition only occurs on the first surface and doesnot occur on the second surface or only occurs on the second surface anddoes not occur on the first surface.

In some embodiments deposition on the first surface of the substraterelative to the second surface of the substrate and/or on the secondsurface of the substrate relative to the first surface is at least about80% selective, which may be selective enough for some particularapplications. In some embodiments the deposition on the first surface ofthe substrate relative to the second surface of the substrate is atleast about 50% selective, which may be selective enough for someparticular application.

In some embodiments the substrate is oxidized following the selectivedeposition of Ni 610 according to methods described herein above. Insome embodiments the oxidation produces OH surface terminations on thefirst surface 640 of the substrate. In some embodiments the oxidationoxidizes the selectively deposited Ni to form Ni(O).

In some embodiments GeO₂ is selectively deposited 620 on a first surface640 of the substrate using a selective deposition process as describedabove wherein the Ge precursor comprises Ge(NMe₂)₄ and the secondreactant comprises H₂O. In some embodiments, the selective deposition ofGeO₂ 620 continues until a desired thickness of GeO₂ is obtained on thefirst surface. In some embodiments selective deposition of GeO₂ 620continues until a desired number of deposition cycles is completed. Forexample, in some embodiments up to about 1-50 deposition cycles forselectively depositing GeO₂ are carried out.

In some embodiments after GeO₂ has been selectively deposited 620 on afirst surface 640 of a substrate relative to a selectively deposited Nisurface of the same substrate any passivation layer or surface treatmentthat may be present on the selectively deposited Ni or Ni(O) surface mayoptionally be removed according to any of the methods described hereinabove.

Although dual selective deposition process 600 illustrated above beganwith selective deposition of Ni 610 before the selective deposition ofGeO₂ 620, one of skill in the art will understand that a dual selectivedeposition process may begin with the selective deposition of eitherGeO₂ or Ni prior to the selective deposition of a second material.

Example 3

A nickel surface can be oxidized to passivate it against subsequentgermanium oxide deposition, forming Ni(O). LEIS analysis showed someincubation, no growth, or very little growth of GeO₂ on a Ni(O) surface:

TABLE 5 Surface fraction of Ni and Ge after GeO₂ ALD on Ni(O) surface.Number of GeO₂ Ni Surface Ge Surface ALD Cycles Fraction (%) Fraction(%) 1 100 0 2 96 0 5 62 2 10 76 2 20 32 4 50 52 40 250 0 60

Dual Selective Growth of Ni and W

Referring to FIG. 7A and FIG. 7B, and in some embodiments dual selectivedeposition of W and Ni 700, 701 can be accomplished on a substratecomprising a first surface 740, 741 and a second different surface 730,731. In some embodiments Ni can be selectively deposited on a secondsurface 730, 731 by a selective deposition process 710, 711 as describedherein above. In some embodiments the Ni precursor used in the selectivedeposition process 710, 711 comprises a nickel betadiketiminatocompound, such bis(4-N-ethylamino-3-penten-2-N-ethyliminato)nickel (II)[Ni(EtN-EtN-pent)2]. In some embodiments W can be selectively depositedon a first surface 740, 741 by a selective deposition process 720, 721as described herein above. In some embodiments the first precursor usedin the selective deposition process is disilane and the W precursor isWF₆.

Referring to FIG. 7A, and in some embodiments W and Ni can beselectively deposited 700 on a substrate comprising a first dielectricsurface 740 and a second, different surface 730. Referring to FIG. 7B,and in some embodiments dual selective deposition of W and Ni 701 can beaccomplished on a substrate comprising a first metal surface 741 and asecond, dielectric surface 731. In some embodiments the first surface741 may comprise Cu, or CuO. In some embodiments the first surface 740may comprise a silicon surface. In some embodiments the first siliconsurface 740 can comprise Si—H terminations. In some embodiments thesecond surface 730, 731 can comprise a hydrophilic surface. In someembodiments the second surface can comprise an OH, NH_(x), or SH_(x)terminated surface. In some embodiments the second surface can comprisea SiO₂ or other dielectric surface.

In some embodiments the substrate is optionally treated to enhanceselective deposition 751 according to the methods described herein aboveprior to beginning selective deposition. In some embodiments the second,CuO surface is exposed to a reducing agent and reduced to a Cu surfaceaccording to methods described herein above prior to the beginning of aselective deposition process. In some embodiments a previously reducedmetal surface may additionally be deactivated according to the methodsdescribed herein above. In some embodiments the previously reducedsurface may be deactivated by exposure to disilane 751 to produce a Si—Hterminated surface.

In some embodiments Ni is selectively deposited 710, 711 on the secondsurface 730, 731 of the substrate relative to the first surface 740, 741of the same substrate according to methods described herein above. Insome embodiments the Ni precursor used in the selective depositionprocess comprises a nickel betadiketiminato compound, suchbis(4-N-ethylamino-3-penten-2-N-ethyliminato)nickel (II)[Ni(EtN-EtN-pent)2].

In some embodiments, the selective deposition of Ni 710, 711 continuesuntil a desired thickness of Ni is obtained on the second surface. Insome embodiments selective deposition of Ni 710, 711 continues until adesired number of deposition cycles is completed. For example, in someembodiments up to about 1-50 deposition cycles for selectivelydepositing Ni are carried out.

In some embodiments after selective deposition of Ni on a second surfaceof the substrate the substrate may optionally be treated to enhanceselective deposition according to the methods described herein above.

In some embodiments W is selectively deposited 720, 721 on a firstsurface 740, 741 of the substrate relative to the selectively depositedNi surface of the same substrate. In some embodiments W is selectivelydeposited 720, 721 according to methods described herein above. In someembodiments the first precursor used in the selective deposition processis disilane and the W precursor is WF₆.

In some embodiments, the selective deposition of W 720, 721 continuesuntil a desired thickness of W is obtained on the first surface. In someembodiments deposition on the first surface 740, 741 of the substraterelative to the second surface 730, 731 of the substrate, and/or on thesecond surface 730, 731 of the substrate relative to the first surface740, 741 of the substrate is at least about 90% selective, at leastabout 95% selective, at least about 96%, 97%, 98% or 99% or greaterselective. In some embodiments deposition only occurs on the firstsurface and does not occur on the second surface or only occurs on thesecond surface and does not occur on the first surface.

In some embodiments deposition on the first surface of the substraterelative to the second surface of the substrate and/or on the secondsurface of the substrate relative to the first surface is at least about80% selective, which may be selective enough for some particularapplications. In some embodiments the deposition on the first surface ofthe substrate relative to the second surface of the substrate is atleast about 50% selective, which may be selective enough for someparticular application.

In some embodiments after W has been selectively deposited 720, 721 on afirst surface of a substrate 740, 741 relative to a selectivelydeposited Ni surface of the same substrate any passivation layer orsurface treatment that may be present on the selectively deposited Nisurface may optionally be removed according to any of the methodsdescribed herein above.

Although the dual selective deposition processes 700, 701 illustratedabove began with selective deposition of Ni 710, 711 before theselective deposition of W 720, 721, one of skill in the art willunderstand that a dual selective deposition process may begin with theselective deposition of either W or Ni prior to the selective depositionof a second material.

Dual Selective Growth of Al and SiO₂

Referring to FIG. 8, and in some embodiments dual selective depositionof an Al film and a SiO₂ film 800 can be accomplished on a substratecomprising a first metal surface 840 and a second dielectric surface830. In some embodiments Al can be selectively deposited on the firstmetal surface 840 by a selective deposition process 810 as describedherein above. In some embodiments the Al precursor used in the dualselective deposition process comprises DMAH or DMEAA.

In some embodiments Al is selectively deposited 810 on a first metalsurface 840 of a substrate. In some embodiments the first metal surface840 comprises a CuO surface. In some embodiments the CuO surface isreduced to a Cu surface prior to selective deposition of Al by exposure850 to a reducing agent according to methods described herein above.

In some embodiments the second surface 830 of the substrate may comprisea dielectric surface as described herein above. In some embodiments thesecond surface 830 of the substrate may comprise, for example a SiO₂. Insome embodiments the second surface of the substrate may comprise MgO,GeO₂, or Al₂O₃ surface. In some embodiments the second surface of thesubstrate may comprise OH, NH_(x), or SH_(x) terminations.

In some embodiments, the selective deposition of Al 810 continues untila desired thickness of Al is obtained on the first surface. In someembodiments selective deposition of the Al continues until a desirednumber of deposition cycles is completed. For example, in someembodiments up to about 1-50 deposition cycles for selectivelydepositing Al are carried out.

In some embodiments, after Al has been selectively deposited on a firstsurface 840 of a substrate relative to a second, dielectric surface 830of the same substrate, the Al surface may optionally be passivatedagainst deposition of SiO₂ by any of the methods described herein above.Additionally, in some embodiments any passivation treatment that wasoptionally provided on the second surface may optionally be removed. Insome embodiments the second surface may optionally be activatedaccording to methods described herein above.

After any optional surface treatment has been provided, SiO₂ isselectively deposited 820 on the second surface 830 of the substraterelative to the selectively deposited Al surface of the same substrateaccording to methods described herein above. In some embodiments SiO₂ isselectively deposited 820 on a second surface 830 of the substrate usinga selective deposition process as described above wherein the Siprecursor comprises H₂Si(NEt₂)₂ and the second reactant comprises O₃.

In some embodiments, the selective deposition of SiO₂ 820 continuesuntil a desired thickness of SiO₂ material is obtained on the secondsurface 830. In some embodiments selective deposition of the SiO₂material continues until a desired number of deposition cycles iscompleted. For example, in some embodiments up to about 1-50 depositioncycles for selectively depositing the SiO₂ material are carried out.

In some embodiments deposition on the first surface 840 of the substraterelative to the second surface 830 of the substrate, and/or on thesecond surface 830 of the substrate relative to the first surface 840 ofthe substrate is at least about 90% selective, at least about 95%selective, at least about 96%, 97%, 98% or 99% or greater selective. Insome embodiments deposition only occurs on the first surface and doesnot occur on the second surface or only occurs on the second surface anddoes not occur on the first surface.

In some embodiments deposition on the first surface of the substraterelative to the second surface of the substrate and/or on the secondsurface of the substrate relative to the first surface is at least about80% selective, which may be selective enough for some particularapplications. In some embodiments the deposition on the first surface ofthe substrate relative to the second surface of the substrate is atleast about 50% selective, which may be selective enough for someparticular application.

In some embodiments after SiO₂ has been selectively deposited 820 on asecond surface 830 of a substrate relative to a selectively deposited Alsurface of the same substrate any passivation layer or surface treatmentthat may be present on the selectively deposited Al surface mayoptionally be removed according to any of the methods described hereinabove. In some embodiments etching of the Al surface 860 is optional andmay be desired, for example, to remove any SiO₂ that has been depositedon the Al surface.

Although dual selective deposition process 800 illustrated above beganwith selective deposition of Al 810 before the selective deposition ofSiO₂ 820, one of skill in the art will understand that a dual selectivedeposition process may proceed with the selective deposition of eitherSiO₂ or Al prior to the selective deposition of a second material.

What is claimed is:
 1. A method for selectively depositing a firstmetallic material on a first surface of a substrate and a seconddielectric material on a second surface of the same substrate, whereinthe first surface is a surface of metal or semiconductor material andthe second surface comprises OH, NH_(x) or SH_(x)-terminations, themethod comprising: selectively depositing the first metallic material onthe first surface of the substrate relative to the second surface of thesubstrate; and selectively depositing the second dielectric material onthe second surface of the substrate relative to the first surface. 2.The method of claim 1, wherein selectively deposing the first metallicmaterial and selectively depositing the second dielectric material isperformed in the same reactor.
 3. The method of claim 1, whereinselectively depositing the first metallic material and selectivelydepositing the second dielectric material is performed without anairbreak in between selectively depositing the first metallic materialand selectively depositing the second material.
 4. The method of claim1, wherein selectively depositing the first metallic material andselectively depositing the second dielectric material is performedwithout further processing in between selectively depositing the firstmetallic material and selectively depositing the second material.
 5. Themethod of claim 1, wherein the first surface comprises Cu, Si—H, W, Ni,Co, Ru or another noble metal.
 6. The method of claim 1, wherein thesecond surface is a surface of a dielectric material.
 7. The method ofclaim 6, additionally comprising treating the second dielectric surfaceto inhibit deposition of the metallic material thereon prior toselectively depositing the first metallic material on a metal.
 8. Themethod of claim 1, wherein the first surface is treated to inhibitdeposition of the dielectric material thereon prior to selectivelydepositing the second dielectric material.
 9. The method of claim 8,wherein the first surface is oxidized.
 10. The method of claim 8,wherein the first surface is passivated.
 11. The method of claim 1,wherein selectively depositing the first material comprises at least onedeposition cycle comprising alternately and sequentially contacting thesubstrate with a first metal precursor and a second reactant.
 12. Themethod of claim 11, wherein from 1 to 50 deposition cycles forselectively depositing the first material are carried out prior toselectively depositing the second material.
 13. The method of claim 1,wherein selectively depositing the second material comprises at leastone deposition cycle comprising alternately and sequentially contactingthe substrate with a first metal precursor and a second reactant. 14.The method of claim 13, wherein from 1 to 50 deposition cycles forselectively depositing the second material are carried out.
 15. Themethod of claim 1, wherein the metallic material is selectivelydeposited on the first surface relative to the second surface with aselectivity of at least 80%.
 16. The method of claim 1, wherein thesecond material is selectively deposited on the second surface relativeto the first surface with a selectivity of at least 80%.
 17. The methodof claim 1, wherein the first metallic material is selected from Sb, Ge,Ru, noble metal, W, Cu, Al, Ni, and Co.
 18. The method of claim 1,wherein the second dielectric material is selected from SbO_(x), GeO₂,BiO_(x), MgO, SiO₂, AlO₂, and TiO₂.
 19. A method for selectivelydepositing two different materials on two different surfaces of asubstrate, wherein a first surface is a surface comprising a metal orsemiconductor material and a second surface comprises OH, NH_(x) orSH_(x)-terminations, the method comprising: selectively depositing afirst material on the first surface of the substrate relative to thesecond surface of the substrate; and selectively depositing a secondmaterial on the second surface of the substrate relative to the firstsurface, wherein at least one of selectively depositing the firstmaterial and selectively depositing the second material is an atomiclayer deposition (ALD) process.
 20. The method of claim 19, whereinselectively deposing the first metallic material and selectivelydepositing the second dielectric material is performed in the samereactor.
 21. The method of claim 19, wherein selectively depositing thefirst metallic material and selectively depositing the second dielectricmaterial is performed without an airbreak in between selectivelydepositing the first metallic material and selectively depositing thesecond dielectric material.
 22. The method of claim 19, whereinselectively depositing the first metallic material and selectivelydepositing the second dielectric material is performed without furtherprocessing in between selectively depositing the first metallic materialand selectively depositing the second dielectric material.
 23. Themethod of claim 19, wherein the first material is a layer of W, thesecond material is a layer of Sb, and the second surface comprises adielectric.
 24. The method of claim 19, wherein the first material is alayer of W, the first surface comprises Cu, the second material is alayer of Sb, and the second surface comprises Si—OH terminations. 25.The method of claim 19, wherein one of selectively depositing the firstmaterial and selectively depositing the second material is a chemicalvapor deposition (CVD) process.
 26. The method of claim 25, wherein oneof selectively depositing the first material and selectively depositingthe second material comprises decomposing the precursor while contactingthe substrate with the precursor.
 27. The method of claim 26, whereinthe first material comprises Ni, Ge, Fe, Co, or TiO₂.
 28. The method ofclaim 27, wherein the second material is Al or Cu.
 29. The method ofclaim 19, wherein the first material is a conducting metallic material,the first surface is a metal or semiconducting surface, the secondmaterial is a dielectric, and the second surface is a surface of adielectric material.
 30. A method for selectively depositing a firstmetallic material on a first metal or semiconductor surface of asubstrate and a second dielectric material on a second surface of thesame substrate, wherein the second surface comprises a surface of amaterial that is not conducting or semiconducting, the methodcomprising: selectively depositing the first metallic material on thefirst surface of the substrate relative to the second surface of thesubstrate; and selectively depositing the second dielectric material onthe second surface of the substrate relative to the first surface. 31.The method of claim 30, wherein selectively deposing the first metallicmaterial and selectively depositing the second dielectric material isperformed in the same reactor.
 32. The method of claim 30, whereinselectively depositing the first metallic material and selectivelydepositing the second dielectric material is performed without anairbreak in between selectively depositing the first metallic materialand selectively depositing the second dielectric material.
 33. Themethod of claim 30, wherein selectively depositing the first metallicmaterial and selectively depositing the second dielectric material isperformed without further processing in between in between selectivelydepositing the first metallic material and selectively depositing thesecond material.
 34. The method of claim 30, wherein the first surfacecomprises Cu, Si—H, Ru, Ni, Al, W, or Co.
 35. The method of claim 30,wherein the second surface is a surface of a dielectric material. 36.The method of claim 30, wherein selectively depositing the seconddielectric material comprises treating second surface to provide OHterminations thereon.
 37. The method of claim 36, wherein selectivelydepositing the first metallic material comprising deactivating thesecond surface prior to depositing the first metallic material.
 38. Themethod of claim 30, wherein selectively depositing the second dielectricmaterial comprises treating the first surface to inhibit deposition ofthe second dielectric material thereon prior to depositing the seconddielectric material.
 39. The method of claim 38, wherein treating toinhibit comprises oxidizing the first surface.
 40. The method of claim38, wherein the first surface comprises Ni and treating to inhibitcomprises oxidizing Ni to form Ni(O).
 41. The method of claim 38,wherein treating to inhibit comprises passivating the first surface. 42.The method of claim 30, wherein selectively depositing the firstmetallic material comprises at least one deposition cycle comprisingalternately and sequentially contacting the substrate with a first metalprecursor and a second reactant.
 43. The method of claim 42, whereinfrom 1 to 50 deposition cycles for selectively depositing the firstmetallic material are carried out prior to selectively depositing thesecond dielectric material.
 44. The method of claim 30, whereinselectively depositing the second dielectric material comprises at leastone deposition cycle comprising alternately and sequentially contactingthe substrate with a first metal precursor and a second reactant. 45.The method of claim 44, wherein from 1 to 50 deposition cycles forselectively depositing the second dielectric material are carried out.46. The method of claim 30, wherein the first metallic material isselected from Sb, Ge, Ru, noble metal, W, Cu and Al.
 47. The method ofclaim 30, wherein the second dielectric material is selected fromSbO_(x), GeO₂, BiO_(x), MgO, SiO₂, AlO₂, and TiO₂,
 48. A method forselectively depositing tungsten on a first surface of a substrate andantimony on a second different surface of the same substrate, the methodcomprising: selectively depositing the tungsten on the first surface ofthe substrate relative to the second surface of the substrate; andselectively depositing the antimony on the second surface of thesubstrate relative to the first surface.
 49. The method of claim 40wherein the first surface is a metal or semiconductor surface and thesecond surface comprises OH, NH_(x) or SH_(x)-terminations.
 50. A methodfor selectively depositing a material comprising nickel on a firstsurface of a substrate and germanium oxide on a second surface differentof the same substrate, the method comprising: selectively depositing thematerial comprising nickel on the first surface of the substraterelative to the second surface of the substrate; and selectivelydepositing the germanium on the second surface of the substrate relativeto the first surface.
 51. The method of claim 50, wherein selectivelydepositing the material comprising nickel comprises providing the firstsurface with OH-terminations and the second surface with H-terminations;and selectively depositing the germanium oxide comprises, afterselectively depositing the nickel, oxidizing a surface of the nickel andthe second surface.
 52. A method for selectively depositing ruthenium ona first surface of a substrate and germanium oxide or silicon dioxide ona second surface of the same substrate, the method comprising:selectively depositing the ruthenium on the first surface of thesubstrate relative to the second surface of the substrate; andselectively depositing the germanium oxide or the silicon dioxide on thesecond surface of the substrate relative to the first surface.
 53. Themethod of claim 53, wherein selectively depositing the ruthenium is doneprior selectively depositing the germanium oxide or silicon dioxide. 54.The method of claim 52, wherein the first surface is metal.
 55. Themethod of claim 52, wherein the second surface is an oxide surface. 56.The method of claim 52, wherein the oxide surface comprises a dielectricsurface material having OH surface terminations.
 57. The method of claim52, wherein selectively depositing the germanium oxide or the silicondioxide on the second surface of the substrate comprises using apassivation precursor.
 58. The method of claim 57, wherein thepassivation precursor selected from HCOOH, a precursor comprising analkylamine, or both.